institut parisien de chimie moléculaire, umr 8232, …...s7 ii. dft calculations xyz coordinates ch...

S1

Supporting Information

C2-Alkylation and Alkenylation of Indoles Catalyzed by a Low-Valent Cobalt Complex in the absence of Reductant

Brendan J. Fallon,[a] Etienne Derat,[a] Muriel Amatore,[a] Corinne Aubert,[a] Fabrice Chemla,[a]

Franck Ferreira,[a] Alejandro Pérez-Luna,[a] and Marc Petit*[a]

Institut Parisien de Chimie Moléculaire, UMR 8232, Université Pierre et Marie Curie-Paris 6,

Case 229, 4 Place Jussieu, 75252 Paris, France

List of the Contents of the Supporting Information

I. General information………………………………………………………………………………………. S2

II. Deuterium and mechanistic studies..…………………………………………………………….S3

III. DFT calculations………………………………………………………………………………………….. S6

IV. Preparation of starting materials…………………………………………………………………. S18

V. Characterization of new compounds …………………………………………………………….S22

VI. 1H NMR Spectra of products…………………………………………………………………………S45

VII. References…………………………………………………………………………………………………. S86

S2

I. General information:

Commercial reagents were purified prior to use following the guidelines of Perrin and

Armarego.1 Toluene was purified by mean of distillation under dry nitrogen atmosphere on

benzophenone/sodium ketyl and degassed by sparging argon. Organic solutions were

concentrated under reduced pressure on a Büchi rotary evaporatory. Chromatographic

purifications of products were accomplished using force-flow chromatography on Davisil

(LC60A) SI 60 Å (40 – 63 μm) silica gel according to the method of Still.2 Thin layer

chromatography (TLC) was performed on Merck 60 F254 silica gel plates. TLC visualization

was performed by fluorescence quenching (λ = 254 nm), dipping in KMnO4 or para-

anisaldehyde stains. Filtrations through Celite were performed using Hyflo Super Cel from

Fluka. 1H NMR spectra were recorded on a Brucker 400 AVANCE or 300 AVANCE (400 and

300 MHz respectively) and are referenced relative to residual CDCl3 protons signals at δ 7.26

ppm. 13C NMR spectra were recorded on a Brucker 400 AVANCE or 300 AVANCE (100 and 75

MHz respectively) and are referenced relative to CDCl3 at δ 77.00 ppm. 19F NMR spectra

were recorded on a Brucker 400 AVANCE (376 MHz) and are referenced relative to CFCl3 at

δ 0.00 ppm. Data are reported as follows: chemical shift (δ ppm), multiplicity (s = singlet, d =

doublet, t = triplet, q = quartet, qt = quintuplet, m = multiplet, bs = broad signal), coupling

constant (Hz) and integration. IR spectra were recorded on a Bruker Tensor 27 (ATR

diamond) and are reported in terms of frequency of absorption (cm-1). High-resolution

Mass spectra were obtained from the Laboratoire Structure et Fonction de Molécules

Bioactives (Université Pierre et Marie Curie, Paris 6).

S3

III. Deuterium and mechanistic experiments:

1H NMR Spectra of deuteriated and non deuteriated indoles

98% deuterium

incorporation

S4

(a) Deuterium labeling experiment (see scheme 2a in article)

Recovery of the starting material showed a significant decrease of the deuterium

content (0.04 H to 0.7H). Deuterium was included into all TWO alkene position alpha

and beta (0.78H). The desired product was isolated with a marginal (<20% )

incorporation of deuterium in the α position. Consistent with this observation the

methyl group was substantially deuteriated >50%

2.47H

0.86H

0.7H

0.78H

0.78H

0.78H

Sm. >98% D

63% 2.47

66% 2.47

22% 2.47

S5

(b) Hydrogen/Deuterium transfer study (see scheme 2b in article)

Deuterium labeled indole 1a-d was reacted with diphenylacetylene 2a in the presence of 50 mol% HCo(PMe3)4. No hydrogen incorporation was observed in the final product. This result suggested that C-H bond activation and functionalization proceeded in a concerted manner for the hydro-complex. This hypothesis was further substantiated by DFT calculations.

S6

(c) Competition experiment (see scheme 3a in article)

S7

II. DFT Calculations

XYZ coordinates

CH activation with diphenylacetylene

Reagent

Co 27.0 -0.43050739 -1.06316304 0.03477350

N 7.0 -1.74982035 0.06607950 -0.88688481

C 6.0 -2.90954971 0.52436191 -0.51064640

C 6.0 -3.56713676 0.18440720 0.72082728

C 6.0 -3.16466618 -0.73964149 1.68446171

C 6.0 -1.17674661 0.52816761 -2.10211468

C 6.0 -0.57751411 -0.40000680 -2.96770215

C 6.0 -1.13193059 1.89500189 -2.44120646

C 6.0 -0.51538187 2.31405044 -3.61578274

C 6.0 0.07561160 1.37912846 -4.48548269

C 6.0 0.03960150 0.01511340 -4.15165758

O 8.0 0.65355867 1.88710332 -5.60361958

C 6.0 1.27025890 1.01134145 -6.52017260

H 1.0 -2.28855395 -1.38734400 1.68647647

H 1.0 -0.61814040 -1.46156156 -2.70870662

H 1.0 -1.56433439 2.63405085 -1.76074278

H 1.0 -0.46581230 3.37299252 -3.88341475

H 1.0 0.48362130 -0.73827410 -4.80446720

H 1.0 0.54841971 0.28396419 -6.94367647

H 1.0 2.10941100 0.45450759 -6.05660057

H 1.0 1.66406918 1.64016938 -7.33446360

P 15.0 0.55180049 0.45107639 1.30222154

C 6.0 2.33587074 0.88802040 1.04976904

C 6.0 -0.20976560 2.14150643 1.33103979

C 6.0 0.52340341 0.01719590 3.10058570

H 1.0 2.68399167 1.64115655 1.78098035

H 1.0 2.46749830 1.28541100 0.02779770

H 1.0 2.95179486 -0.02254700 1.14285111

H 1.0 -0.11012090 2.59823656 0.33045560

H 1.0 0.26406890 2.80249405 2.08007717

H 1.0 -1.28649569 2.04407477 1.55580962

H 1.0 1.01517475 0.78974700 3.72000265

H 1.0 1.02615309 -0.95431072 3.24484229

S8

H 1.0 -0.52796400 -0.08995340 3.42109466

C 6.0 -0.85512441 -2.88244700 -0.17431040

C 6.0 0.11441560 -2.75851226 0.70622140

C 6.0 -1.70346844 -3.85216761 -0.84697241

C 6.0 0.86974692 -3.49693203 1.70451200

C 6.0 -1.41974914 -5.23646736 -0.82654870

C 6.0 -2.25162601 -6.14653969 -1.48127627

C 6.0 -3.39046931 -5.69839191 -2.16506529

C 6.0 -3.68552756 -4.32975245 -2.19457030

C 6.0 -2.84757495 -3.41740513 -1.54889631

C 6.0 2.19629884 -3.14315009 2.03046632

C 6.0 0.28511679 -4.57528830 2.40888238

C 6.0 2.91122055 -3.83728147 3.00999403

C 6.0 2.31291604 -4.89635658 3.70392060

C 6.0 0.99429250 -5.25937366 3.39812064

H 1.0 -0.53119272 -5.58579445 -0.29178190

H 1.0 -2.01339746 -7.21563816 -1.45797038

H 1.0 -4.04361439 -6.41445971 -2.67487097

H 1.0 -4.57273579 -3.97182465 -2.72811699

H 1.0 -3.06284237 -2.34502697 -1.57049096

H 1.0 2.66075659 -2.31330323 1.48984492

H 1.0 -0.74328530 -4.86281204 2.16910338

H 1.0 3.94307303 -3.54800367 3.23744941

H 1.0 2.86990285 -5.43598843 4.47674847

H 1.0 0.51661009 -6.08715248 3.93376231

N 7.0 -4.07351828 -0.78877568 2.70526409

C 6.0 -5.10096312 0.10620690 2.44329071

C 6.0 -4.82106066 0.73867428 1.20005906

C 6.0 -6.24289227 0.40343869 3.19754744

C 6.0 -7.12066936 1.35903609 2.68569469

C 6.0 -6.86264610 1.99946821 1.45437145

C 6.0 -5.72293949 1.69861126 0.70924962

C 6.0 -3.99437571 -1.64856315 3.86677861

H 1.0 -5.53623247 2.20435023 -0.24321650

H 1.0 -7.57166576 2.74480748 1.08027005

H 1.0 -8.02422047 1.61577225 3.24777174

H 1.0 -6.44093466 -0.09498210 4.15061045

H 1.0 -4.86967707 -2.32191968 3.91435552

H 1.0 -3.08032632 -2.25924587 3.80240464

H 1.0 -3.96028781 -1.05008638 4.79565620

H 1.0 -3.44697118 1.21486843 -1.17948341

Transition state

S9

Co 27.0 0.68895888 0.36415109 0.51567990

N 7.0 -1.40281188 -0.72720528 0.41212341

C 6.0 -1.77015984 -0.98581129 1.63717484

C 6.0 -0.90189862 -0.62169349 2.70382214

C 6.0 0.32752150 -0.00308970 2.37684608

C 6.0 -2.21546340 -0.98335481 -0.69523108

C 6.0 -1.60702574 -1.37111986 -1.90187061

C 6.0 -3.61921835 -0.81614941 -0.68985552

C 6.0 -4.37313366 -1.04376018 -1.83717394

C 6.0 -3.75332212 -1.44366896 -3.03435731

C 6.0 -2.35797429 -1.60574031 -3.05785799

O 8.0 -4.57594347 -1.63479578 -4.10176229

C 6.0 -4.01979971 -2.02500153 -5.33458471

H 1.0 1.35410833 -0.86405110 1.04385614

H 1.0 -0.52100128 -1.49050665 -1.91923976

H 1.0 -4.11918926 -0.47518149 0.22193611

H 1.0 -5.45780087 -0.90411282 -1.83856869

H 1.0 -1.84029007 -1.91092312 -3.96937156

H 1.0 -3.49982643 -3.00211740 -5.26339531

H 1.0 -3.30550599 -1.27020454 -5.72340202

H 1.0 -4.86015368 -2.11858845 -6.04121113

P 15.0 -0.32008311 2.37512231 0.64006311

C 6.0 -1.84562135 2.60358810 -0.36661071

C 6.0 -0.89656150 2.88327837 2.31855512

C 6.0 0.71040529 3.82501745 0.14660300

H 1.0 -2.27894664 3.60782671 -0.20792720

H 1.0 -2.58114290 1.83136046 -0.08795140

H 1.0 -1.60213065 2.47465992 -1.43276656

H 1.0 -1.59232199 2.12056637 2.70689988

H 1.0 -1.39511526 3.86906099 2.29310918

H 1.0 -0.03327700 2.92442870 3.00425410

H 1.0 0.15781809 4.77264977 0.28016949

H 1.0 1.01185119 3.72151852 -0.90924633

H 1.0 1.62403953 3.84844637 0.76637369

C 6.0 1.90830207 -0.41864580 -0.80851948

C 6.0 1.37018585 0.62160438 -1.33515918

C 6.0 2.79205966 -1.54606128 -1.06135237

C 6.0 1.27839041 1.48630357 -2.49556422

C 6.0 3.52202868 -1.57658255 -2.27081323

C 6.0 4.37106848 -2.64395142 -2.56331730

C 6.0 4.50990534 -3.70405531 -1.65690005

C 6.0 3.79090691 -3.68583679 -0.45659381

C 6.0 2.94103503 -2.61693311 -0.16154380

C 6.0 0.09374670 1.56117022 -3.25811648

C 6.0 2.37922359 2.27950239 -2.88557649

S10

C 6.0 0.01588170 2.40225315 -4.37095118

C 6.0 1.10986459 3.19401431 -4.74136782

C 6.0 2.29186773 3.12612176 -3.99383092

H 1.0 3.41018271 -0.74864542 -2.97758389

H 1.0 4.92918444 -2.65115404 -3.50546503

H 1.0 5.17581511 -4.54188156 -1.88766694

H 1.0 3.89087582 -4.51154804 0.25537089

H 1.0 2.37401628 -2.60353589 0.77421921

H 1.0 -0.75802761 0.93582588 -2.97778964

H 1.0 3.30276728 2.22919965 -2.30088806

H 1.0 -0.91085410 2.43965840 -4.95317745

H 1.0 1.04297149 3.85762525 -5.60929346

H 1.0 3.15567255 3.73675919 -4.27737331

N 7.0 0.99016720 0.24474400 3.54822612

C 6.0 0.22723749 -0.17629570 4.64264917

C 6.0 -0.98426688 -0.73703182 4.14257669

C 6.0 0.50992131 -0.09923460 6.00761938

C 6.0 -0.44695500 -0.59901643 6.89915371

C 6.0 -1.65006721 -1.15783668 6.42723608

C 6.0 -1.92677462 -1.23096871 5.05849218

C 6.0 2.29202700 0.86045587 3.65264440

H 1.0 -2.86650610 -1.66911733 4.70717096

H 1.0 -2.38087320 -1.54221702 7.14632559

H 1.0 -0.25588530 -0.55458927 7.97616386

H 1.0 1.44597471 0.33529359 6.37060022

H 1.0 3.00546646 0.19372690 4.17208672

H 1.0 2.66161394 1.05553961 2.63346767

H 1.0 2.23970771 1.81508863 4.21045113

H 1.0 -2.72766137 -1.49373829 1.85173285

Product

Co 27.0 0.49056050 0.41661689 0.63541931

N 7.0 -1.42685401 -0.64168519 0.50573182

C 6.0 -1.90377235 -0.83428079 1.71087086

C 6.0 -1.10888100 -0.45467609 2.82495785

C 6.0 0.14318590 0.13483830 2.53509617

C 6.0 -2.19932461 -0.91899228 -0.63271618

C 6.0 -1.58517003 -1.49261999 -1.75789857

C 6.0 -3.57489967 -0.60937738 -0.71999592

C 6.0 -4.29964018 -0.87635279 -1.87782848

C 6.0 -3.67440987 -1.45813489 -2.99444699

C 6.0 -2.30627990 -1.76824224 -2.92364979

O 8.0 -4.46462965 -1.67681408 -4.08015394

S11

C 6.0 -3.88070512 -2.15738225 -5.26778173

H 1.0 1.68815374 -0.97396982 0.45376709

H 1.0 -0.52002859 -1.72853839 -1.70795214

H 1.0 -4.07387638 -0.12751471 0.12644340

H 1.0 -5.36147547 -0.62530190 -1.95145965

H 1.0 -1.78562057 -2.22061753 -3.76989269

H 1.0 -3.46787000 -3.17921138 -5.14277458

H 1.0 -3.07211971 -1.48941326 -5.62932205

H 1.0 -4.68421841 -2.18793654 -6.02128267

P 15.0 -0.20298889 2.48080778 0.63622522

C 6.0 -1.71512628 2.72727394 -0.38428071

C 6.0 -0.69454819 3.21189952 2.25832748

C 6.0 0.95071870 3.75473380 -0.03372960

H 1.0 -2.07256627 3.77141571 -0.32851329

H 1.0 -2.50271654 2.04194427 -0.03037040

H 1.0 -1.48499346 2.47084045 -1.43097198

H 1.0 -1.45758426 2.56615400 2.72505283

H 1.0 -1.09130847 4.23652220 2.13908291

H 1.0 0.18131430 3.23299623 2.92870784

H 1.0 0.49444851 4.76093149 -0.00825660

H 1.0 1.21505213 3.49488473 -1.07259285

H 1.0 1.87708044 3.76085806 0.56699389

C 6.0 1.93493176 -0.69157052 -0.63280272

C 6.0 1.24095726 0.34605911 -1.12611055

C 6.0 2.88448119 -1.67933345 -1.16729033

C 6.0 1.30397987 1.06028259 -2.39615440

C 6.0 3.28228307 -1.68784654 -2.52172756

C 6.0 4.17553663 -2.64984441 -2.99490619

C 6.0 4.69352055 -3.62688875 -2.13439369

C 6.0 4.30294037 -3.63449097 -0.79085708

C 6.0 3.40947866 -2.67260861 -0.31529149

C 6.0 0.15764000 1.21348667 -3.20439434

C 6.0 2.49726200 1.69294918 -2.81081009

C 6.0 0.20871730 1.95465779 -4.38772917

C 6.0 1.39580154 2.58447766 -4.78108740

C 6.0 2.53939247 2.45011330 -3.98387384

H 1.0 2.88006973 -0.93905210 -3.20719790

H 1.0 4.46931267 -2.63884377 -4.04986668

H 1.0 5.39384031 -4.37962008 -2.51053691

H 1.0 4.69487095 -4.39590359 -0.10837790

H 1.0 3.10416698 -2.68954110 0.73713249

H 1.0 -0.77267408 0.72766721 -2.90018249

H 1.0 3.39365911 1.58789098 -2.19188857

H 1.0 -0.69201529 2.04857349 -5.00370598

H 1.0 1.43023372 3.17495465 -5.70227528

S12

H 1.0 3.47461104 2.93705750 -4.28034925

N 7.0 0.73324031 0.42777160 3.73420978

C 6.0 -0.08853590 0.05066680 4.80251026

C 6.0 -1.27740908 -0.52025110 4.25925112

C 6.0 0.12433940 0.16924050 6.17766953

C 6.0 -0.88316733 -0.29051760 7.03385210

C 6.0 -2.06413054 -0.85922998 6.51901293

C 6.0 -2.26946855 -0.97795850 5.14098072

C 6.0 2.02508187 1.05275714 3.89366031

H 1.0 -3.19274926 -1.42343438 4.75658369

H 1.0 -2.83414626 -1.21423614 7.21186495

H 1.0 -0.74863738 -0.21040060 8.11739826

H 1.0 1.04454112 0.60761452 6.57511091

H 1.0 2.73534083 0.38219360 4.41368961

H 1.0 2.41972589 1.28392613 2.89159346

H 1.0 1.94405985 1.98916066 4.47789717

H 1.0 -2.89572501 -1.29544330 1.85511446

CH activation with styrene

Reagent

Co 27.0 -0.32944560 -1.20587468 -0.17270251

N 7.0 -1.68083775 -0.15348800 -1.07243717

C 6.0 -2.84837961 0.23338120 -0.61421889

C 6.0 -3.35095739 -0.14598051 0.67396468

C 6.0 -2.78233528 -1.03727639 1.58398914

C 6.0 -1.19168460 0.42914751 -2.27140641

C 6.0 -0.55607331 -0.37512329 -3.22821379

C 6.0 -1.26379633 1.81782186 -2.50870061

C 6.0 -0.72582281 2.37274313 -3.66533732

C 6.0 -0.09753380 1.55794811 -4.62427711

C 6.0 -0.01730020 0.17459010 -4.39586830

O 8.0 0.39973301 2.19387412 -5.71668720

C 6.0 1.05261564 1.44219315 -6.71364689

H 1.0 -1.92288995 -1.70140195 1.48565316

H 1.0 -0.50205928 -1.45014393 -3.05003023

H 1.0 -1.72241426 2.46864820 -1.75928187

H 1.0 -0.76713169 3.44994521 -3.84853125

H 1.0 0.45828861 -0.49012050 -5.11940622

H 1.0 0.37707800 0.69275922 -7.17397738

H 1.0 1.94729805 0.92066622 -6.31682777

H 1.0 1.37008440 2.15961361 -7.48708439

P 15.0 0.51052719 0.30981341 1.23922098

S13

C 6.0 2.34267569 0.56216192 1.17766559

C 6.0 -0.10616170 2.04553342 1.05568886

C 6.0 0.23710570 0.02126540 3.04727387

H 1.0 2.67494726 1.34428346 1.88502395

H 1.0 2.63648963 0.85112458 0.15318459

H 1.0 2.84279680 -0.38939220 1.42541897

H 1.0 0.14510991 2.41297126 0.04530880

H 1.0 0.32550281 2.72669029 1.81203926

H 1.0 -1.20648575 2.04115438 1.15312481

H 1.0 0.76855600 0.77412510 3.65774059

H 1.0 0.59202039 -0.98832822 3.31568313

H 1.0 -0.84380949 0.08296850 3.25960970

C 6.0 -0.23378900 -3.08157158 -0.81014812

C 6.0 0.80637121 -2.84655094 0.16175839

C 6.0 0.77588832 -3.31002235 1.56000662

C 6.0 1.91824961 -3.16184521 2.38281488

C 6.0 -0.36687729 -3.88734651 2.16302466

C 6.0 1.91240275 -3.53000736 3.72890615

C 6.0 0.76199120 -4.07947540 4.31094122

C 6.0 -0.37098029 -4.26512146 3.50902987

H 1.0 2.83196259 -2.74563694 1.94348526

H 1.0 -1.26392519 -4.05900097 1.56065965

H 1.0 2.81800461 -3.39362335 4.33034754

H 1.0 0.75523692 -4.37545013 5.36451721

H 1.0 -1.27068877 -4.72376299 3.93509102

N 7.0 -3.51130748 -1.06028628 2.74999905

C 6.0 -4.58235312 -0.19098739 2.62730551

C 6.0 -4.52268887 0.40092149 1.33484983

C 6.0 -5.59088516 0.12253420 3.54883337

C 6.0 -6.55523491 1.05092204 3.15676594

C 6.0 -6.51339102 1.65135014 1.87936842

C 6.0 -5.50610399 1.33573294 0.96784002

C 6.0 -3.21666336 -1.85516238 3.92282891

H 1.0 -5.48503304 1.80828977 -0.01908300

H 1.0 -7.28592348 2.37563372 1.60260117

H 1.0 -7.35831690 1.31759262 3.85113525

H 1.0 -5.62280321 -0.34357250 4.53753710

H 1.0 -4.01404047 -2.59910846 4.10757351

H 1.0 -2.26224852 -2.38254714 3.77371073

H 1.0 -3.12810493 -1.20802796 4.81437683

H 1.0 -3.46812868 0.90875590 -1.22143328

H 1.0 0.08141670 -3.22470975 -1.85637605

H 1.0 -1.08900690 -3.72683311 -0.55466968

H 1.0 1.83037424 -2.70503402 -0.21999530

S14

Transition state

Co 27.0 0.67349100 -0.30276969 0.37903970

N 7.0 -1.44786739 -0.45858559 -0.54665279

C 6.0 -2.30885363 -0.35370111 0.43323240

C 6.0 -1.82919800 -0.25335759 1.76648045

C 6.0 -0.42624220 -0.17101160 1.96210146

C 6.0 -1.83483160 -0.35743499 -1.88642979

C 6.0 -1.12603772 -1.08224344 -2.86017108

C 6.0 -2.86125445 0.50663710 -2.33374667

C 6.0 -3.17076635 0.61653519 -3.68602443

C 6.0 -2.46361089 -0.12771089 -4.64632940

C 6.0 -1.43187666 -0.98096842 -4.22020245

O 8.0 -2.83653569 0.05411610 -5.94186831

C 6.0 -2.15136385 -0.63860881 -6.95780993

H 1.0 0.34621480 -1.51278222 1.30990505

H 1.0 -0.31789130 -1.73854876 -2.53060818

H 1.0 -3.40070701 1.12462652 -1.60973644

H 1.0 -3.95664549 1.29358399 -4.03270197

H 1.0 -0.85647321 -1.57075810 -4.93641424

H 1.0 -2.24715781 -1.73800766 -6.84616756

H 1.0 -1.07384288 -0.37599280 -6.98221540

H 1.0 -2.61461258 -0.33504680 -7.91033363

P 15.0 1.03285158 1.68498731 -0.45918670

C 6.0 1.27099836 1.75274062 -2.28717756

C 6.0 -0.31989771 2.90884495 -0.19391450

C 6.0 2.53460622 2.55517292 0.16906179

H 1.0 1.42230546 2.78819656 -2.64363265

H 1.0 0.38628429 1.31454146 -2.78009486

H 1.0 2.15268278 1.14280236 -2.54770184

H 1.0 -1.24047685 2.51150775 -0.65559310

H 1.0 -0.08216170 3.89308167 -0.63690603

H 1.0 -0.50168413 3.01780152 0.88888699

H 1.0 2.66599727 3.54029322 -0.31481749

H 1.0 3.42034221 1.92535114 -0.02659690

H 1.0 2.44591212 2.69467258 1.26058674

C 6.0 1.13199234 -2.32418537 0.47480139

C 6.0 1.88023841 -1.61661732 -0.57619709

C 6.0 3.24811792 -1.12031281 -0.36016840

C 6.0 4.04241085 -0.71500432 -1.45904636

C 6.0 3.79790735 -0.92900121 0.93109828

C 6.0 5.29513311 -0.12826671 -1.27884674

C 6.0 5.81149769 0.07126150 0.00936600

C 6.0 5.05291033 -0.34150970 1.11044705

H 1.0 3.65538740 -0.86462963 -2.47309852

S15

H 1.0 3.22754622 -1.23599601 1.81326616

H 1.0 5.87943649 0.17515101 -2.15448594

H 1.0 6.79375029 0.53264040 0.15033939

H 1.0 5.44171715 -0.20434050 2.12539291

N 7.0 -0.21784990 -0.06150210 3.31540155

C 6.0 -1.43136609 -0.06253960 4.00840282

C 6.0 -2.48256588 -0.18101691 3.05360508

C 6.0 -1.67499483 0.04164600 5.38012075

C 6.0 -3.00773668 0.02502840 5.80693913

C 6.0 -4.06158495 -0.09397470 4.88024521

C 6.0 -3.81069660 -0.19781549 3.50890017

C 6.0 1.07252383 0.09266480 3.94621539

H 1.0 -4.64048386 -0.29064870 2.80070591

H 1.0 -5.09492016 -0.10561250 5.24196386

H 1.0 -3.23265409 0.10416900 6.87539482

H 1.0 -0.85472000 0.13181420 6.09830904

H 1.0 1.31101441 -0.77022821 4.59704113

H 1.0 1.83616042 0.17387460 3.15625238

H 1.0 1.10158908 1.00972772 4.56409073

H 1.0 -3.39500427 -0.33518529 0.23395750

H 1.0 0.36489001 -3.02327108 0.11105670

H 1.0 1.72048354 -2.76720595 1.29568875

H 1.0 1.63714099 -1.86397755 -1.61595678

Product

Co 27.0 0.32818481 0.34248430 0.15410520

N 7.0 -1.49462998 -0.90100503 0.39422381

C 6.0 -1.73605669 -1.03350079 1.67805815

C 6.0 -0.81804758 -0.49364191 2.61349368

C 6.0 0.26913741 0.25015649 2.09147334

C 6.0 -2.48651433 -1.19479537 -0.55245429

C 6.0 -2.14155912 -1.80895364 -1.76813555

C 6.0 -3.84066725 -0.83092350 -0.36873469

C 6.0 -4.79624939 -1.08233774 -1.34891129

C 6.0 -4.43575525 -1.70509362 -2.55608749

C 6.0 -3.09397173 -2.06828332 -2.75823545

O 8.0 -5.43766642 -1.90019774 -3.45565009

C 6.0 -5.14355803 -2.51217985 -4.68866158

H 1.0 1.37589669 -1.06872106 0.11397880

H 1.0 -1.10341096 -2.10293913 -1.93160295

H 1.0 -4.13652325 -0.31231239 0.54834980

H 1.0 -5.84091663 -0.79046768 -1.20930648

H 1.0 -2.77492571 -2.55492091 -3.68183804

S16

H 1.0 -4.74854517 -3.54029918 -4.55632448

H 1.0 -4.41177702 -1.92288554 -5.27852821

H 1.0 -6.09245777 -2.56383657 -5.24629831

P 15.0 -0.77553552 2.22771311 -0.00647640

C 6.0 -1.86565912 2.36167955 -1.48533535

C 6.0 -1.94813359 2.57775354 1.37275934

C 6.0 0.22577751 3.77447414 -0.08022810

H 1.0 -2.43748164 3.30749583 -1.48463309

H 1.0 -2.56281447 1.50595903 -1.49124563

H 1.0 -1.24369597 2.31092525 -2.39332676

H 1.0 -2.64249349 1.72747815 1.47533882

H 1.0 -2.52061677 3.50493407 1.18934059

H 1.0 -1.38594174 2.66436481 2.31746387

H 1.0 -0.42158550 4.66627455 -0.16442131

H 1.0 0.90823752 3.73031783 -0.94556242

H 1.0 0.83486068 3.85346246 0.83722472

C 6.0 1.47758114 -1.10478449 -1.05514073

C 6.0 0.86055791 0.07119570 -1.75252211

C 6.0 1.72227895 1.20629692 -2.12204814

C 6.0 1.40388012 2.04121494 -3.21802521

C 6.0 2.84814382 1.57332206 -1.34338403

C 6.0 2.14600539 3.18879294 -3.50304961

C 6.0 3.24359035 3.54393816 -2.70730448

C 6.0 3.59049201 2.72180605 -1.62874413

H 1.0 0.55643028 1.77282083 -3.85829639

H 1.0 3.13601303 0.95478421 -0.48589030

H 1.0 1.86881649 3.81192088 -4.36047935

H 1.0 3.82557201 4.44342136 -2.93074870

H 1.0 4.44963741 2.97779202 -0.99909258

N 7.0 0.96780479 0.73945129 3.16093636

C 6.0 0.37945861 0.34250119 4.36867380

C 6.0 -0.76583099 -0.44765720 4.05824566

C 6.0 0.76231188 0.62221831 5.68196774

C 6.0 -0.02522640 0.09924160 6.71503019

C 6.0 -1.16163838 -0.68163830 6.43086290

C 6.0 -1.53740442 -0.96035480 5.11271667

C 6.0 2.14731550 1.56910515 3.07306123

H 1.0 -2.42176199 -1.57255280 4.90814018

H 1.0 -1.75982165 -1.07866633 7.25764084

H 1.0 0.24773830 0.30027941 7.75595903

H 1.0 1.64606631 1.22917974 5.89960766

H 1.0 3.02444243 1.07131994 3.52854991

H 1.0 2.35422635 1.76104355 2.00793791

H 1.0 1.99264419 2.53540277 3.59008479

H 1.0 -2.65756011 -1.53425729 2.02252722

S17

H 1.0 0.99946511 -2.06323910 -1.30702412

H 1.0 2.57221246 -1.19289088 -1.17405891

H 1.0 0.08638400 -0.16673081 -2.49203753

Energetic data

diphenylacetylene

E (u.a.) ZPC (u.a.) S DE

(kcal/mol)

DH

(kcal/mol)

DG

(kcal/mol)

Reagent -3223.131768 0.6011422 1.02431 0.00 0.00 0.00

TS -3223.112064 0.595739 0.97544 12.36 8.97 12.46

Product -3223.137614 0.6012092 0.99585 -3.67 -3.63 -1.60

Styrene

E (u.a.) ZPC (u.a.) S DE

(kcal/mol)

DH

(kcal/mol)

DG

(kcal/mol)

Reagent -2993.608204 0.5422316 0.87555 0.00 0.00 0.00

TS -2993.589622 0.5383477 0.89237 11.66 9.22 8.02

Product -2993.615607 0.5428832 0.88294 -4.65 -4.24 -4.76

S18

Iv. Preparation of starting materials:

General procedure (A) for the preparation of indole precursors:

Indole precursors were prepared through N-alkylation of indole-3-carboxaldehyde with

methyl iodide, benzyl bromide or alkyl bromide with NaH as base in DMF. The

corresponding carbonyl compounds were condensed with para-anisidine in toluene with MS

4Å to afford the corresponding indole substrates which were purified by precipitation from

pentane/Et2O. The 1H NMR spectrum of all compounds showed good agreement with the

literature data.

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-1H-indol-3-yl)methanimine (1a)3

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-1H-indol-3-yl-2-d)methanimine (1a-d)3

(E)-1-(1-Benzyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1b)3

(E)-1-(5-Methoxy-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1d)3

(E)-1-(5-Fluoro-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1h)3

(E)-1-(1-(But-3-en-1-yl)-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (4a)4

(E)-1-(1-((E)-Hex-3-en-1-yl)-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (4c)4

(E)-N-(4-Methoxyphenyl)-1-(1-(2-methylbut-3-en-1-yl)-1H-indol-3-yl)methanimine (4d)4

(E)-1-(1,7-Dimethyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1c)

Pale yellow solid (53 %). mp 142-144 °C. 1H NMR (400 MHz,

CDCl3) δ 8.64 (s, 1H), 8.35 (ddd, J = 7.9, 1.4, 0.7 Hz, 1H), 7.42 (s,

1H), 7.27 – 7.23 (m, 2H), 7.16 (dd, J = 7.9, 7.2 Hz, 1H), 7.03 (dt, J

= 7.1, 1.1 Hz, 1H), 6.98 – 6.93 (m, 2H), 4.11 (s, 3H), 3.86 (s, 3H),

2.79 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 157.3, 152.6, 146.7,

135.5, 135.2, 127.2, 125.9, 123.1, 121.8 (2C), 121.6, 121.3,

120.0, 114.3 (2C), 55.5, 37.3, 19.6. IR (thin film): max = 2989,

1619, 1545, 1242, 744 cm-1. HRMS (ESI): calculated for

C18H19N2O [M+ H]+: 279.1492; found 279.1499.

S19

(E)-1-(5-(Benzyloxy)-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1e)

White solid (44 %). mp 157-159 °C. 1H NMR (400 MHz, CDCl3) δ

8.63 (s, 1H), 8.16 (d, J = 2.5 Hz, 1H), 7.55 (m, 2H), 7.48 – 7.40

(m, 3H), 7.39 – 7.33 (m, 1H), 7.30 – 7.23 (m, 3H), 7.08 (dd, J =

8.9, 2.5 Hz, 1H), 7.00 – 6.94 (m, 2H), 5.21 (s, 2H), 3.87 (s, 3H),

3.82 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 157.2, 154.8, 152.7,

146.7, 137.5, 134.3, 133.1, 128.5 (2C), 127.8 (2C), 127.7, 126.5,

121.8 (2C), 114.7, 114.3 (2C), 114.0, 110.2, 105.4, 70.7, 55.5,

33.4. IR (thin film): max = 2978, 1598, 1467, 1376, 1250, 1052, 896 cm-1. HRMS (ESI):

calculated for C24H23N2O2 [M+ H]+: 371.1754; found 371.1748.

Methyl (E)-3-(((4-methoxyphenyl)imino)methyl)-1-methyl-1H-indole-6-carboxylate (1f)

white solid (44 %). mp 175-177 °C. 1H NMR (400 MHz, CDCl3) δ

8.67 (s, 1H), 8.50 (dd, J = 8.4, 0.7 Hz, 1H), 8.15 (dd, J = 1.5, 0.7

Hz, 1H), 7.99 (dd, J = 8.4, 1.4 Hz, 1H), 7.70 (s, 1H), 7.29 – 7.23

(m, 2H), 7.00 – 6.91 (m, 2H), 3.99 (s, 3H), 3.94 (s, 3H), 3.86 (s,

3H). 13C NMR (100 MHz, CDCl3) δ 167.8, 157.6, 151.9, 148.8,

137.3, 136.2, 131.1 129.5, 124.8, 122.4, 121.8 (2C), 121.7,

114.3 (2C), 111.8, 55.5, 52.1, 33.5. IR (thin film): max = 2946,

1701, 1594, 1500, 1266, 891, 879 cm-1. HRMS (ESI): calculated for C19H19N2O3 [M+ H]+:

323.1390; found 323.1397.

(E)-1-(5-Isocyano-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1g)

yellow solid (73 %). mp 190-192 °C. 1H NMR (400 MHz, CDCl3)

δ 8.96 (dd, J = 1.6, 0.7 Hz, 1H), 8.63 (s, 1H), 7.63 – 7.51 (m, 2H),

7.41 (dd, J = 8.6, 0.7 Hz, 1H), 7.31 – 7.20 (m, 2H), 7.05 – 6.92

(m, 2H), 3.90 (s, 3H), 3.87 (s, 3H). 13C NMR (100 MHz, CDCl3) δ

157.8, 151.1, 145.6, 139.2, 135.4, 128.4, 126.2, 125.6, 121.9

(2C), 120.4, 115.9, 114.4 (2C), 110.3, 104.6, 55.5, 33.5.

IR (thin film): max = 3289, 2938, 2217, 1623, 1539, 1388,

1121, 834 cm-1. HRMS (ESI): calculated for C18H16N3O [M+ H]+: 290.1288; found 290.1285.

S20

(E)-1-(6-Chloro-1-methyl-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (1i)

Yellow solid (60 %). mp 125-127 °C. 1H NMR (400 MHz, CDCl3)

δ 8.60 (s, 1H), 8.45 (dd, J = 8.5, 0.5 Hz, 1H), 7.45 (s, 1H), 7.35

(dd, J = 1.8, 0.6 Hz, 1H), 7.29 – 7.27 (m, 1H), 7.26 – 7.22 (m,

2H), 6.98 – 6.93 (m, 2H), 3.86 (s, 3H), 3.80 (s, 3H).

13C NMR (100 MHz, CDCl3) δ 157.52, 152.13, 146.28, 138.28,

134.39, 129.18, 124.45, 123.41, 122.05, 121.87 (2C), 115.30,

114.34 (2C), 109.60, 55.52, 33.31. IR (thin film): max = 2966, 1987, 1564, 1480, 1104, 811

cm-1. HRMS (ESI): calculated for C17H16N2OCl [M+ H]+: 299.0946; found 299.0957

(E)-1-(1-(But-3-en-1-yl)-1H-indol-3-yl)-N-(4-methoxyphenyl)ethan-1-imine (4b)

Orange solid (53 %). mp 69-71 °C. 1H NMR (400 MHz, CDCl3) δ

8.36 – 8.22 (m, 1H), 7.64 (s, 1H), 7.33 – 7.12 (m, 3H), 6.75 –

6.62 (m, 2H), 6.61 – 6.47 (m, 2H), 5.70 (m, 1H), 5.11 – 4.91 (m,

2H), 4.21 – 4.04 (m, 2H), 3.66 (s, 3H), 2.54 (m, 2H), 2.44 (s, 3H).

13C NMR (100 MHz, CDCl3) δ 161.8, 155.4, 145.4, 137.0, 134.2,

131.0, 123.5, 122.7, 121.3 (2C), 117.8, 117.1, 116.6, 114.1 (2C),

109.4, 60.4, 55.5, 46.2, 34.3, 17.9. IR (thin film): max = 2936,

1636, 1526, 1465, 1340, 823 cm-1. HRMS (ESI): calculated for C21H23N2O [M+ H]+: 319.1805;

found 319.1802

S21

(E)-1-(1-(But-3-en-1-yl)-5-methoxy-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (4e)

Yellow solid (41 %). mp 72-74 °C. 1H NMR (400 MHz, CDCl3) δ

8.54 (s, 1H), 7.93 (d, J = 2.6 Hz, 1H), 7.42 (s, 1H), 7.24 – 7.07 (m,

3H), 6.89 – 6.81 (m, 3H), 5.70 (dd, J = 17.3, 10.0 Hz, 1H), 5.09 –

4.90 (m, 2H), 4.11 (t, J = 7.1 Hz, 2H), 3.84 (s, 3H), 3.76 (s, 3H),

2.53 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 157.2, 155.6, 152.8,

146.8, 134.0, 133.1, 132.1, 126.7, 121.8 (2C), 118.0, 116.4,

114.3 (2C), 113.4, 110.4, 103.8, 55.8, 55.5, 46.5, 34.2. IR (thin

film): max = 3011, 2937, 1616, 1499, 1288, 1104, 745 cm-1. HRMS (ESI): calculated for

C21H23N2O2 [M+ H]+: 335.1754; found 335.1751.

Methyl (E)-1-(but-3-en-1-yl)-3-(((4-methoxyphenyl)imino)methyl)-1H-indole-6-carboxylate

(4f)

Yellow solid (41 %). mp 83-85 °C. 1H NMR (400 MHz, CDCl3) δ

8.58 (s, 1H), 8.41 (dd, J = 8.4, 0.7 Hz, 1H), 8.07 (dd, J = 1.5, 0.7

Hz, 1H), 7.95 (dd, J = 8.4, 1.4 Hz, 1H), 7.62 (s, 1H), 7.17 – 7.13

(m, 2H), 6.89 – 6.84 (m, 2H), 5.80 – 5.64 (m, 1H), 5.06 – 4.96

(m, 2H), 4.23 (t, J = 7.1 Hz, 2H), 3.90 (s, 3H), 3.77 (s, 3H), 2.63 –

2.52 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 167.8, 162.0, 152.0,

136.5 (2C), 135.1, 133.6, 129.7, 125.1, 124.8, 122.4, 121.8 (2C),

118.3, 115.3, 114.3 (2C), 111.9, 55.5, 52.1, 46.5, 34.3. IR (thin film): max = 2947, 1706, 1616,

1535, 1462, 1286, 878, 789 cm-1. HRMS (ESI): calculated for C22H23N2O3 [M+ H]+: 363.1691;

found 363.1703.

Synthesis of catalysts:

Co(PMe3)4 and HCo(PMe3)4 were synthesised according to literature methods and showed

good agreement with the literature data.5,6 Note care should be taken when handling these

catalysts as they are combustible in air.

S22

V. Characterization of new compounds.

General procedure B: Cobalt catalysed hydroarylation of internal alkynes:

To a sealed tube under argon were added Co(PMe3)4 (5 mol %), imine (0.5mmol) and alkyne

(0.6 mmol). Degassed toluene (1 mL) was added and the resulting solution was heated at

170 °C for 1 h in the microwave (absorption level normal). The reaction mixture was then

filtered through a plug of celite washing with ethyl acetate (3 x 10 ml). The crude product

was purified by silica chromatography to yield the desired product.

(E)-1-(2-((Z)-1,2-Diphenylvinyl)-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine

(3aa)7

The general procedure (B) was applied to (E)-N-(4-methoxyphenyl)-1-(1-

methyl-1H-indol-3-yl)methanimine (1a, 132.0 mg, 0.50 mmol, 1.0 eq.)

and diphenylacetylene (2a, 106.8 mg, 0.60 mmol, 1.2 eq.). Silica gel

chromatography (eluent pentane/EtOAc 80/20) afforded the title

compound (3aa) as a yellow solid (218.7 mg, 99 %). mp; 79-82 oC. 1H

NMR (400 MHz, CDCl3) δ 8.74 – 8.69 (m, 1H), 8.38 (s, 1H), 7.51 (s, 1H),

7.41 – 7.34 (m, 8H), 7.20 – 7.16 (m, 3H), 7.09 – 7.04 (m, 2H), 6.94 – 6.89

(m, 2H), 6.81 – 6.83 (m, 2H), 3.79 (s, 3H), 3.49 (s, 3H).13C NMR (100 MHz,

CDCl3) δ 157.1, 153.7, 146.8, 143.7, 140.9, 137.9, 135.9, 134.4, 129.7, 128.9 (2C), 128.8 (2C),

128.7 (2C), 128.2, 128.2, 126.4 (2C), 125.7, 123.3, 123.1, 121.9, 121.8 (2C), 114.1 (2C), 112.8,

109.5, 55.4, 30.4. IR (thin film): max = 3055, 2934, 1615, 1500, 1243, 1076, 777, 695 cm-1.

HRMS (ESI): calculated for C31H26N2O [M+ H]+: 443.2118; found 443.2118.

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-((Z)-1-phenyl-2-(trimethylsilyl)vinyl)-1H-indol-3-

yl)methanimine (3ab)


methyl-1H-indol-3-yl)methanimine (1a, 132.0 mg, 0.50 mmol, 1.0 eq.) and

trimethyl(phenylethynyl)silane (2b, 104.1 mg, 0.60 mmol, 1.2 eq.). Silica gel

chromatography (eluent pentane/EtOAc 80/20) afforded the title compound

(3ab) as a yellow oil (202.1 mg, 92 %) as a mixture of stereoisomers 90/10

S23

anti/syn as determined by 1H NMR. The characteristic peaks for the minor isomer as

determined by 1H NMR are as follows: δ 6.23 (s, 1H), 3.83 (s, 3H), 3.41 (s, 3H). Major isomer:

1H NMR (400 MHz, CDCl3) δ 8.76 (ddd, J = 6.6, 3.0, 1.8 Hz, 1H), 8.51 (s, 1H), 7.38 – 7.27 (m,

8H), 7.21 – 7.17 (m, 2H), 6.99 (s, 1H), 6.91 – 6.87 (m, 2H), 3.81 (s, 3H), 3.49 (s, 3H), -0.10 (s,

9H). 13C NMR (100 MHz, CDCl3) δ 158.0, 154.9, 147.7, 146.4, 145.3, 141.0, 138.5, 138.2,

129.6 (2C), 129.4, 127.0 (2C), 126.3, 124.1, 124.1, 122.8 (2C), 122.7, 115.2 (2C), 115.1, 110.1,

56.3, 31.2, 0.0 (3C). IR (thin film): max = 2951, 1615, 1574, 1499, 1464, 1242, 909 cm-1.

HRMS (ESI): calculated for C31H26N2O [M+ H]+: 439.2200; found 439.2196.

(Z)-1-Methyl-2-(1-phenylhex-1-en-1-yl)-1H-indole-3-carbaldehyde (3ac)

A modified version of procedure (B) was applied to (E)-N-(4-methoxyphenyl)-

1-(1-methyl-1H-indol-3-yl)methanimine (1a, 132.0 mg, 0.50 mmol, 1.0 eq.) and

hex-1-yn-1-ylbenzene (2c, 95 mg, 0.60 mmol, 1.2 eq.). The resulting mixture

was quenched with 3M HCl (1.0 mL). The resulting mixture was then stirred at

room temperature for 1 h, and then extracted with ethyl acetate (3 x 10 mL).

The combined organic layer was dried over MgSO4 and concentrated under reduced

pressure. Silica gel chromatography (eluent pentane/EtOAc 80/20) afforded the title

compound (3ac) as a yellow oil (218.7 mg, 65 %) as a mixture of stereoisomers 88/12

anti/syn as determined by 1H NMR. The characteristic peaks for the minor isomer as

determined by 1H NMR are as follows: δ 9.89 (s, 1H), 6.06 (t, J = 7.5 Hz, 1H).

Major Isomer: 1H NMR (400 MHz, CDCl3) δ 9.77 (s, 1H), 8.40 – 8.32 (m, 1H), 7.35 – 7.11 (m,

6H), 7.05 – 6.98 (m, 1H), 6.78 – 6.73 (m, 1H), 6.64 (t, J = 7.5 Hz, 1H), 3.42 (d, J = 1.2 Hz, 3H),

2.02 (m, J = 7.4 Hz, 2H), 1.48 – 1.14 (m, 4H), 0.77 (t, J = 7.3 Hz, 3H). 13C NMR (100 MHz,

CDCl3) δ 186.1, 149.3, 138.9, 138.0, 129.1, 128.8, 128.6, 128.0 (2C), 127.9, 125.9 (2C), 125.1,

123.6, 123.1, 122.2, 115.8, 109.7, 31.3, 30.3, 22.3, 13.8. IR (thin film): max = 2929, 1652,

1464, 1382, 1046, 751 cm-1. HRMS (ESI): calculated for C22H23NNaO [M+ H]+: 340.1672;

found 340.1660.

S24

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-((Z)-1-(pyridin-3-yl)-2-(trimethylsilyl)vinyl)-1H-

indol-3-yl)methanimine (3ad)

The general procedure (B) was applied to (E)-N-(4-methoxyphenyl)-1-

(1-methyl-1H-indol-3-yl)methanimine (1a, 132.0 mg, 0.50 mmol, 1.0

eq.) and 3-((trimethylsilyl)ethynyl)pyridine (2d, 105.1 mg, 0.60 mmol,

1.2 eq.). Silica gel chromatography (eluent pentane/EtOAc 75/25)

afforded the title compound (3ad) as a yellow oil (217.3 mg, 99 %). 1H

NMR (400 MHz, CDCl3) δ 8.77 – 8.71 (m, 1H), 8.70 – 8.66 (m, 1H), 8.52

(dd, J = 4.8, 1.6 Hz, 1H), 8.49 (s, 1H), 7.48 (ddd, J = 8.0, 2.4, 1.6 Hz, 1H),

7.40 – 7.32 (m, 3H), 7.25 – 7.14 (m, 3H), 7.07 (s, 1H), 6.92 – 6.85 (m, 2H), 3.80 (s, 3H), 3.50

(s, 3H), -0.09 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 158.3, 154.3, 150.4, 148.3, 147.6, 144.8,

142.6, 141.3, 138.3, 136.7, 134.3, 126.4, 124.5, 124.4, 124.2, 123.0, 122.8 (2C), 115.6, 115.2

(2C), 110.3, 56.4, 31.3, -0.0 (3C). IR (thin film): max = 2951, 1615, 1498, 1464, 1437, 1408,

1241, 1034, 835, 748 cm-1. HRMS (ESI): calculated for C27H30N3OSi [M+ H]+: 440.2153; found

440.2143.


yl)methanimine (3ae)


methyl-1H-indol-3-yl)methanimine (1a, 132.0 mg, 0.50 mmol, 1.0 eq.)

and oct-4-yne (2e, 66.3 mg, 0.60 mmol, 1.2 eq.). Silica gel


compound (3ae) as a yellow oil (185.1 mg, 99 %) as a mixture of

stereoisomers 79/21 anti/syn as determined by 1H NMR. The

characteristic peaks for the minor isomer as determined by 1H NMR are

as follows: δ 8.67 (s, 1H), 5.80 (t, J = 7.4 Hz, 1H).

Major isomer: 1H NMR (400 MHz, CDCl3) δ 8.79 (m, 1H), 8.58 (s, 1H), 7.48 – 7.36 (m, 3H),

7.34 – 7.25 (m, 2H), 7.07 – 6.97 (m, 2H), 6.09 (m, 1H), 3.92 (s, 3H), 3.75 (d, J = 6.2 Hz, 3H),

2.58 – 2.34 (m, 2H), 1.96 (m, 1H), 1.70 – 1.33 (m, 4H), 1.12 (m, 1H), 1.02 (m, 3H), 0.92 (t, J =

7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 157.1, 154.0, 147.3, 146.2, 137.6, 135.9, 130.1,

S25

125.6, 122.7, 122.7, 121.8 (2C), 121.6, 114.3 (2C), 112.1, 109.2, 55.5, 41.0, 31.8, 30.3, 22.4,

21.5, 13.9, 13.8. IR (thin film): max = 2956, 2869, 1614, 1498, 1463, 1370, 1241, 1035, 747

cm-1. HRMS (ESI): calculated for C25H31N2O [M+ H]+: 375.2431; found 375.2420.


yl)methanimine (3af)

The general procedure (B) was applied to (E)-N-(4-methoxyphenyl)-1-

(1-methyl-1H-indol-3-yl)methanimine (1a, 132.0 mg, 0.50 mmol, 1.0

eq.) and dec-5-yne (2f, 83.1 mg, 0.60 mmol, 1.2 eq.). Silica gel


compound (3af) as a yellow oil (164.4 mg, 82 %) as a mixture of

stereoisomers 78/22 anti/syn as determined by 1H NMR. The

characteristic peaks for the minor isomer as determined by 1H NMR

are as follows: δ 8.63 (s, 1H), 5.76 (s, 1H).

Major isomer: 1H NMR (400 MHz, CDCl3) δ 8.75 (m, 1H), 8.55 (d, J = 0.8 Hz, 1H), 7.43 – 7.34

(m, 3H), 7.29 – 7.24 (m, 2H), 7.04 – 6.97 (m, 2H), 6.05 (m, 1H), 3.89 (s, 3H), 3.72 (d, J = 5.8

Hz, 3H), 2.58 – 2.30 (m, 2H), 2.04 – 1.86 (m, 2H), 1.68 – 1.19 (m, 7H), 1.06 (m, 1H), 0.97 –

0.90 (m, 3H), 0.90 – 0.82 (m, 3H). 13C NMR (100 MHz, CDCl3) δ 157.1, 154.0, 147.3, 146.2,

137.6, 136.0, 130.1, 125.6, 122.7, 122.6, 121.8 (2C), 121.6, 114.3 (2C), 112.1, 109.2, 55.5,

38.6, 31.5, 30.4, 30.3, 29.5, 22.5, 22.3, 13.9, 13.8. IR (thin film): max = 2926, 1614, 1498,


found 403.2748.

General procedure (C) : Cobalt catalysed intermolecular hydroarylation of alkenes:

To a sealed tube under argon were added Co(PMe3)4 (10 mol %), imine (0.5mmol) and

alkene (0.6-1.0 mmol). Degassed toluene (1 mL) was added and the resulting solution was

heated at 170 °C for 1 h in the microwave (absorption level normal). The reaction mixture

was then filtered through a plug of celite washing with ethyl acetate (3 x 10 ml). The crude

product was purified by silica chromatography to yield the desired product.

S26

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-(1-phenylethyl)-1H-indol-3-yl)methanimine (3ag)

The general procedure (C) was applied to (E)-N-(4-methoxyphenyl)-1-

(1-methyl-1H-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0 eq.)

and styrene (2g, 62 mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography

(eluent pentane/EtOAc 90/10) afforded the title compound (3ag) as a

yellow foam (182 mg, 99 %). mp 59-61 °C. 1H NMR (400 MHz, CDCl3) δ

8.79 (s, 1H), 8.70 – 8.64 (m, 1H), 7.39 – 7.29 (m, 8H), 7.20 – 7.15 (m,

2H), 6.95 – 6.91 (m, 2H), 5.15 (q, J = 7.4 Hz, 1H), 3.85 (s, 3H), 3.50 (s,

3H), 1.89 (d, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3δ 157.2, 153.0,

148.2, 147.1, 141.9, 137.6, 128.6 (2C), 127.1 (2C), 126.5, 125.9, 122.7, 122.2, 121.8 (2C),

121.6, 114.2 (2C), 111.8, 108.8, 55.5, 34.5, 30.9, 18.6. IR (thin film): max = 3053, 2940, 1613,

1498, 1242, 783 cm-1. HRMS (ESI): calculated for C25H25N2O [M+ H]+: 369.1973; found

369.1961

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-(1-(p-tolyl)ethyl)-1H-

indol-3-yl)methanimine (3ah)

The general procedure (C) was applied to (E)-N-(4-

methoxyphenyl)-1-(1-methyl-1H-indol-3-yl)methanimine (1a, 132

mg, 0.50 mmol, 1.0 eq.) and 1-methyl-4-vinylbenzene (2h, 70 mg,

0.6 mmol, 1.2 eq.). Silica gel chromatography on silica (eluent

pentane/EtOAc 90/10) afforded the title compound (3ah) as a

yellow oil (182 mg, 99 %). 1H NMR (400 MHz, CDCl3) δ 8.77 (s,

1H), 8.69 – 8.64 (m, 1H), 7.32 – 7.27 (m, 3H), 7.20 – 7.12 (m, 6H), 6.95 – 6.89 (m, 2H), 5.10

(q, J = 8 Hz, 1H), 3.83 (s, 3H), 3.49 (s, 3H), 2.35 (d, J = 0.7 Hz, 3H), 1.85 (d, J = 7.4 Hz, 3H). 13C

NMR (100 MHz, CDCl3) δ 157.2, 153.1, 148.5, 147.2, 138.9, 137.6, 136.1, 129.3 (2C), 127.0

(2C), 125.9, 122.6, 122.3, 121.8 (2C), 121.6, 114.2 (2C), 111.8, 108.8, 55.5, 34.2, 30.9, 20.9,

18.7. IR (thin film): max = 2936, 1612, 1574, 1497, 1240, 1061, 964, 777 cm-1. HRMS (ESI):

calculated for C26H26N2O [M+ H]+: 383.2122; found 383.2118.

S27

(E)-N-(4-Methoxyphenyl)-1-(2-(1-(3-methoxyphenyl)ethyl)-1-

methyl-1H-indol-3-yl)methanimine (3ai)



mg, 0.50 mmol, 1.0 eq.) and 1-methoxy-3-vinylbenzene (2i, 68

mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography on silica

(eluent pentane/EtOAc 85/15) afforded the title compound (3ai)

as a yellow oil (179.6 mg, 90 %). 1H NMR (400 MHz, CDCl3) δ 8.81 (s, 1H), 8.72 – 8.62 (m,

1H), 7.29 (dt, J = 16.3, 5.8 Hz, 4H), 7.20 (d, J = 8.4 Hz, 2H), 6.99 – 6.86 (m, 4H), 6.82 (d, J = 8.5

Hz, 1H), 5.13 (d, J = 7.4 Hz, 1H), 3.86 (s, 3H), 3.79 (s, 3H), 3.52 (s, 3H), 1.87 (d, J = 7.3 Hz, 3H).

13C NMR (100 MHz, CDCl3) δ 160.0, 157.2, 152.9, 148.0, 147.2, 143.7, 137.6, 129.7, 125.9,

122.7 (2C), 122.2, 121.8, 121.6, 119.6, 114.3 (2C), 113.5, 111.8, 111.3, 108.8, 55.5, 55.2,

34.5, 31.0, 18.6. IR (thin film): max = 2939, 1612, 1499, 1468, 1242, 1035, 912, 749 cm-1.

HRMS (ESI): calculated for C26H27N2O2 [M+ H]+: 399.2067; found 399.2055.

(E)-N-(4-Methoxyphenyl)-1-(2-(1-(2-methoxyphenyl)ethyl)-1-methyl-1H-indol-3-

yl)methanimine (3aj)

The general procedure (C) was applied to (E)-N-(4-methoxyphenyl)-1-(1-methyl-1H-indol-3-

yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0 eq.) and 1-methoxy-2-vinylbenzene (2j, 83 mg,

0.6 mmol, 1.2 eq.). Silica gel chromatography on silica (eluent pentane/EtOAc 90/10)

afforded a mixture of the title compound (3aj) and the product of linear addition as a yellow

foam (169 mg, 85 %). The branched/linear ratio was determined to be 76/24 by 1H NMR.

S28

Characteristic peaks for the linear product are 3.33 (t, J = 7.8 Hz, 2H) and 3.03 (t, J = 7.8 Hz,

2H). Note: NMR signals are only assigned to the major isomer. mp 68-79 °C 1H NMR (400

MHz, CDCl3) δ 8.78 (s, 1H), 8.71 – 8.67 (m, 1H), 7.51 – 7.46 (m, 1H), 7.36 – 7.26 (m, 5H), 7.10

– 7.05 (m, 3H), 6.93 – 6.85 (m, 2H), 4.96 (q, J = 7.4 Hz, 1H), 3.85 (s, 3H), 3.78 (s, 3H), 3.68 (s,

3H), 1.84 (d, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 157.2, 157.0, 154.0, 149.1, 147.3,

137.1, 130.8, 128.1, 127.2, 126.0, 122.8, 122.2, 121.9 (2C), 121.8, 121.4, 120.4, 114.1 (2C),

111.0, 110.8, 108.7, 55.4, 31.0, 30.1, 19.8. IR (thin film): max = 2936, 1592, 1497, 1242,

1033, 748 cm-1. HRMS (ESI): calculated for C26H27N2O2 [M+ H]+: 399.2067; found 399.2069

(E)-1-(2-(1-(4-Fluorophenyl)ethyl)-1-methyl-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3ak)

The general procedure (C) was applied to (E)-N-(4-methoxyphenyl)-

1-(1-methyl-1H-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0

eq.) and 1-fluoro-4-vinylbenzene (2k, 73 mg, 0.6 mmol, 1.2 eq.).

Silica gel chromatography on silica (eluent pentane/EtOAc 90/10)

afforded the title compound (3ak) as a yellow oil (162.6 mg, 84 %).

1H NMR (400 MHz, CDCl3) δ 8.67 (s, 1H), 8.58 – 8.48 (m, 1H), 3.75 –

3.72 (m, 3H), 7.24 – 7.13 (m, 5H), 7.09 – 7.05 (m, 2H), 6.96 – 6.90 (m, 2H), 6.85 – 6.81 (m,

2H), 5.06 (q, J = 7.9 Hz, 1H), 3.38 (s, 3H), 1.77 (d, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ

161.5 (d, J = 245.5 Hz), 157.3, 152.7, 147.7, 147.1, 137.7 (d, J = 3.2 Hz), 137.6 , 130.06 (d, J =

7.9 Hz), 128.64 (d, J = 8.0 Hz), 125.9, 122.8, 122.2, 121.8 (2C), 121.7, 115.6, 115.3, 114.3

(2C), 111.8, 108.8, 55.5, 33.9, 30.9, 18.8. 19F NMR (376 MHz, CDCl3) δ -116.2. IR (thin film):

max = 2939, 1574, 1439, 1179, 1003, 831, 778 cm-1 HRMS (ESI): calculated for C25H23N2OF

[M+ H]+: 387.1868; found 387.1867.

S29

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-(1-(naphthalen-2-

yl)ethyl)-1H-indol-3-yl)methanimine (3al)



mg, 0.50 mmol, 1.0 eq.) and 2-vinylnaphthalene (2l, 93 mg, 0.6

mmol, 1.2 eq.). Silica gel chromatography on silica (eluent

pentane/EtOAc 90/10) afforded the title compound (3al) as a

yellow oil (136.0 mg, 65 %). 1H NMR (400 MHz, CDCl3) δ 8.81 (s,

1H), 8.69 – 8.63 (m, 1H), 7.85 – 7.79 (m, 3H), 7.77 (d, J = 8.6 Hz, 1H), 7.55 – 7.45 (m, 2H),

7.36 – 7.26 (m, 4H), 7.15 – 7.07 (m, 2H), 6.89 – 6.83 (m, 2H), 5.28 (q, J = 7.3 Hz, 1H), 3.81 (s,

3H), 3.48 (s, 3H), 1.98 (d, J = 7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 157.2, 153.0, 147.9,

147.1, 139.5, 137.7, 133.4, 132.1, 128.4, 127.8, 127.6, 126.3, 126.1, 125.9, 125.8, 124.8,

122.7, 122.2, 121.8 (2C), 121.7, 114.2 (2C), 111.9, 108.8, 55.5, 34.8, 30.9, 18.6. IR (thin film):

max = 3003, 1677, 1468, 1106, 908, 730 cm-1 HRMS (ESI): calculated for C29H26N2O [M+ H]+:

418.2120; found 418.2118.

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-(1-phenylpropyl)-1H-indol-3-yl)methanimine

(3am)



mg, 0.50 mmol, 1.0 eq.) and (E)-prop-1-en-1-ylbenzene (2m, 78

mg, 0.6 mmol, 1.2 eq.). Silica gel chromatography (eluent

pentane/EtOAc 70/30) afforded the title compound (3am) as a

yellow oil (105.3 mg, 55 %). 1H NMR (400 MHz, CDCl3) δ 8.85 (s,

1H), 8.73 – 8.67 (m, 1H), 7.38 – 7.29 (m, 8H), 7.23 – 7.16 (m, 2H),

6.99 – 6.91 (m, 2H), 4.87 (dd, J = 10.2, 5.9 Hz, 1H), 3.86 (s, 3H), 3.53 (s, 3H), 2.55 (m, 1H),

2.24 (m, 1H), 1.05 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 157.2, 153.2, 147.2, 146.5,

141.4, 137.6, 128.6 (2C), 127.5 (2C), 126.6, 125.9, 122.6, 122.3, 121.8 (2C), 121.6, 114.3 (2C),

S30

113.3, 108.8, 55.5, 42.2, 30.9, 25.6, 12.7. IR (thin film): max = 2962, 1613, 1240, 1150, 806

cm-1. HRMS (ESI): calculated for C26H27N2O [M+ H]+: 383.2118; found 383.2122.

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-(1-(pyridin-4-yl)ethyl)-1H-indol-3-yl)methanimine

(3an)


(1-methyl-1H-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0

eq.) and 4-vinylpyridine (2n, 65 mg, 0.6 mmol, 1.2 eq.). Silica gel


compound (3an) as a yellow foam (182 mg, 99 %). mp 63-65 °C. 1H

NMR (400 MHz, CDCl3) δ 8.65 (s, 1H), 8.46 (m, 3H), 7.25 – 7.16 (m,

3H), 7.11 (dt, J = 4.6, 1.2 Hz, 2H), 7.07 – 7.00 (m, 2H), 6.85 – 6.76 (m, 2H), 5.18 – 5.09 (m,

1H), 3.71 (s, 3H), 3.36 (s, 3H), 1.76 (d, J = 7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 157.4,

152.2, 151.3, 150.1 (2C), 146.8, 145.7, 137.5, 126.0, 123.0 (2C), 122.3 (2C), 121.8 (3C), 114.3

(2C), 112.1, 109.0, 55.5, 34.1, 31.1, 17.8. IR (thin film): max =2941, 1612, 1440, 1241, 1061,

749, 730 cm-1. HRMS (ESI): calculated for C24H24N3O [M+ H]+: 370.1914; found 370.1920.

(E)-1-(1-Benzyl-2-(1-phenylethyl)-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (3bg)

The general procedure (C) was applied to (E)-1-(1-benzyl-1H-

indol-3-yl)-N-(4-methoxyphenyl)methanimine (1b, 170 mg, 0.50

mmol, 1.0 eq.) and styrene (2g, 62 mg, 0.6 mmol, 1.2 eq.). Silica

gel chromatography (eluent pentane/EtOAc 85/15) afforded the

title compound (3bg) as a yellow solid (204 mg, 92 %). mp 178-

180 °C. 1H NMR (400 MHz, CDCl3) δ 8.63 – 8.59 (m, 2H), 7.23 –

7.05 (m, 11H), 7.02 – 6.97 (m, 2H), 6.86 – 6.82 (m, 2H), 6.82 –

6.77 (m, 2H), 5.16 (s, 2H), 4.84 (q, J = 7.3 Hz, 1H), 3.73 (s, 3H),

1.61 (d, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 157.2, 153.3, 148.5, 147.0, 142.2, 137.3,

136.8, 128.7 (2C), 128.6 (2C), 127.4, 127.2 (2C), 126.6, 126.2, 125.8 (2C), 123.0, 122.6, 121.9,

121.8 (2C), 114.2 (2C), 112.2, 109.7, 55.5, 47.3, 35.1, 19.7. IR (thin film): max = 3056, 1614,

S31


445.2273.

(E)-1-(1,7-Dimethyl-2-(1-phenylethyl)-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine

(3cg)

The general procedure (C) was applied (E)-1-(1,7-dimethyl-

1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1c, 139

mg, 0.50 mmol, 1.0 eq.) and styrene (2g, 62 mg, 0.6 mmol,

1.2 eq.). Silica gel chromatography (eluent pentane/EtOAc

80/20) afforded the title compound (3cg) as a yellow oil (96

mg, 50 %). 1H NMR (400 MHz, CDCl3) δ 8.68 (s, 1H), 8.46

(ddd, J = 8.0, 1.3, 0.7 Hz, 1H), 7.31 – 7.15 (m, 5H), 7.11 – 7.01

(m, 3H), 6.90 (dt, J = 7.1, 1.2 Hz, 1H), 6.86 – 6.78 (m, 2H), 5.11 (q, J = 7.4 Hz, 1H), 3.74 (s, 3H),

3.65 (s, 3H), 2.66 (s, 3H), 1.78 (d, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 157.1, 153.0,

148.5, 147.2, 142.1, 136.4, 128.7 (2C), 127.0 (2C), 126.4, 126.9, 126.2, 121.8 (2C), 121.6,

120.6, 120.1, 114.2 (2C), 111.7, 55.5, 34.3, 34.1, 20.7, 18.3. IR (thin film): max = 2928, 1613,

1538, 1290. 895 cm-1.. HRMS (ESI): calculated for C26H27N2O [M+ H]+: 383.2118; found

383.2113.

(E)-1-(5-Methoxy-1-methyl-2-(1-phenylethyl)-1H-indol-3-

yl)-N-(4-methoxyphenyl)methanimine (3dg)

The general procedure (C) was applied (E)-1-(5-methoxy-1-

methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine

(1d, 139 mg, 0.50 mmol, 1.0 eq.) and styrene (2g, 62 mg,

0.6 mmol, 1.2 eq.). Silica gel chromatography (eluent

pentane/EtOAc 80/20) afforded the title compound (3dg)

as a yellow oil (189 mg, 95 %). 1H NMR (400 MHz, CDCl3) δ

8.64 (s, 1H), 8.14 (d, J = 2.5 Hz, 1H), 7.27 – 7.10 (m, 5H), 7.09 – 7.02 (m, 3H), 6.87 – 6.76 (m,

3H), 4.93 (q, J = 7.3 Hz, 1H), 3.83 (s, 3H), 3.72 (s, 3H), 3.35 (s, 3H), 1.75 (d, J = 7.4 Hz, 3H).

S32

13C NMR (100 MHz, CDCl3) δ 157.2, 155.9, 153.1, 148.6, 147.2, 142.0, 132.7, 128.7 (2C),

127.1 (2C), 126.6, 126.4, 121.8 (2C), 114.3 (2C), 112.7, 111.6, 109.6, 104.3, 55.9, 55.5, 34.6,

31.0, 18.7. IR (thin film): max = 3085, 1558, 1158, 1028, 885, 718 cm-1.. HRMS (ESI):

calculated for C26H27N2O2 [M+ H]+: 399.2067; found 399.2078.

(E)-1-(5-(Benzyloxy)-1-methyl-2-(1-phenylethyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3eg)

The general procedure (C) was applied to (E)-1-(5-

(benzyloxy)-1-methyl-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (1e, 186 mg, 0.50 mmol, 1.0

eq.) and styrene (2g, 62 mg, 0.6 mmol, 1.2 eq.). Silica gel

chromatography (eluent pentane/EtOAc 85/15) afforded

the title compound (3eg) as a yellow foam (234 mg, 99 %).

mp 62-64 °C. 1H NMR (400 MHz, CDCl3) δ 8.77 (s, 1H), 8.38 (d, J = 2.6 Hz, 1H), 7.60 – 7.54 (m,

2H), 7.43 (t, J = 7.5 Hz, 2H), 7.39 – 7.26 (m, 6H), 7.19 (t, J = 8.3 Hz, 3H), 7.05 (dd, J = 8.8, 2.6

Hz, 1H), 6.99 – 6.92 (m, 2H), 5.23 (s, 2H), 5.07 (q, J = 7.3 Hz, 1H), 3.87 (s, 3H), 3.49 (s, 3H),

1.89 (d, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 157.2, 155.0, 153.0, 148.6, 147.2, 142.0,

137.7, 132.8, 128.7 (2C), 128.5 (2C), 127.8 (2C), 127.7, 127.1 (2C), 126.6, 126.4, 121.8 (2C),

114.3 (2C), 113.3, 111.6, 109.6, 105.8, 70.8, 55.5, 34.6, 31.0, 18.7. IR (thin film): max = 3031,

1612, 1497, 1288, 1105, 735 cm-1. HRMS (ESI): calculated for C32H31N2O2 [M+ H]+: 475.2380;

found 475.2395.

Methyl (E)-3-(((4-methoxyphenyl)imino)methyl)-1-methyl-2-(1-phenylethyl)-1H-indole-6-

carboxylate (3fg)

The general procedure (C) was applied to methyl (E)-3-(((4-

methoxyphenyl)imino)methyl)-1-methyl-1H-indole-6-carboxylate

(1f, 161 mg, 0.50 mmol, 1.0 eq.) and styrene (2g, 62 mg, 0.6 mmol,

1.2 eq.). Silica gel chromatography (eluent pentane/EtOAc 85/15)

afforded the title compound (3fg) as a yellow foam (209 mg, 99 %).

mp 68-79 °C. 1H NMR (400 MHz, CDCl3) δ 8.64 (s, 1H), 8.55 (d, J =

S33

8.4 Hz, 1H), 7.96 – 7.92 (m, 1H), 7.86 (dd, J = 8.4, 1.5 Hz, 1H), 7.28 – 7.20 (m, 2H), 7.21 – 7.12

(m, 3H), 7.08 – 7.01 (m, 2H), 6.86 – 6.77 (m, 2H), 5.03 (q, J = 7.4 Hz, 1H), 3.85 (s, 3H), 3.71 (s,

3H), 3.44 (s, 3H), 1.77 (d, J = 7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 167.9, 157.4, 152.4,

151.0, 146.7, 141.5, 137.1, 129.6, 128.8 (2C), 127.1, 126.8, 124.2, 122.7 (2C), 121.9 (2C),

121.8, 114.3 (2C), 112.1, 111.1, 55.5, 52.0, 34.8, 31.1, 18.5. IR (thin film): max = 2948, 1707,

1567, 1433, 1236, 783 cm-1. HRMS (ESI): calculated for C27H27N2O3 [M+ H]+: 427.2016; found

427.2020

(E)-3-(((4-Methoxyphenyl)imino)methyl)-1-methyl-2-(1-phenylethyl)-1H-indole-5-

carbonitrile (3gg)


methoxyphenyl)imino)methyl)-1-methyl-1H-indole-5-carbonitrile (1g,

144 mg, 0.50 mmol, 1.0 eq.) and styrene (2g, 62 mg, 0.6 mmol, 1.2 eq.).

Silica gel chromatography (eluent pentane/EtOAc 85/15) afforded the

title compound (3gg) as a yellow oil (162 mg, 82 %). 1H NMR (400 MHz,

CDCl3) δ 9.08 (dd, J = 1.7, 0.7 Hz, 1H), 8.72 (s, 1H), 7.51 (dd, J = 8.5, 1.7

Hz, 1H), 7.38 – 7.25 (m, 6H), 7.19 – 7.11 (m, 2H), 6.96 – 6.89 (m, 2H),

5.10 (q, J = 7.9 Hz, 1H), 3.83 (s, 3H), 3.52 (s, 3H), 1.88 (d, J = 7.4 Hz, 3H). 13C NMR (100 MHz,

CDCl3) δ 157.7, 151.6, 150.0, 146.1, 141.1, 139.2, 128.9 (2C), 128.1, 127.0 (2C), 126.9, 125.8,

125.7, 121.9 (2C), 120.7, 114.3 (2C), 112.5, 109.7, 104.6, 55.5, 34.8, 31.2, 18.7. IR (thin film):

max = 2942, 2220, 1614, 1500, 1289, 1106 cm-1. HRMS (ESI): calculated for C26H24N3O [M+

H]+: 394.1914; found 394.1909.

(E)-1-(5-Fluoro-1-methyl-2-(1-phenylethyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3hg)

The general procedure (c) was applied to (E)-1-(5-fluoro-1-

methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1h, 141

mg, 0.50 mmol, 1.0 eq.) and styrene (2g, 0.62 mg, 0.6 mmol, 1.2

eq.). Silica gel chromatography (eluent pentane/EtOAc 90/10)

S34

afforded the title compound (3hg) as a yellow foam (182 mg, 99 %). mp 63-65 °C. 1H NMR

(400 MHz, CDCl3) δ 8.64 (s, 1H), 8.52 (dd, J = 8.7, 5.7 Hz, 1H), 7.29 – 7.17 (m, 5H), 7.10 – 7.02

(m, 2H), 6.94 (td, J = 9.1, 2.3 Hz, 1H), 6.88 – 6.78 (m, 3H), 4.95 (q, J = 7.4 Hz, 1H), 3.74 (s, 3H),

3.34 (s, 3H), 1.77 (d, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 160.3 (d, J = 239.3 Hz),

157.3, 152.6, 148.65 (d, J = 3.0 Hz), 146.8, 141.8, 138.0 (d, J = 11.7 Hz), 128.7 (2C), 127.0

(2C), 126.7, 123.5 (d, J = 9.6 Hz), 122.2, 121.8 (2C), 114.3 (2C), 112.0, 109.8 (d, J = 23.4 Hz),

95.6 (d, J = 26.5 Hz), 55.5, 34.6, 31.1, 18.8. 19F NMR (376 MHz, CDCl3) δ -119.2. IR (thin film):

max = 2939, 1614, 1499, 1242, 1059, 984, 828 cm-1. HRMS (ESI): calculated for C25H24FN2O

[M+ H]+: 387.1867; found 387.1854.

(E)-1-(2-(2-Cyclopentylethyl)-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine

(3ao)


(1-methyl-1H-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0

eq.) and vinylcyclopentane (2o, 96 mg, 1.00 mmol, 2.0 eq.). Silica gel


compound (3ao) as a yellow solid (126 mg, 70 %). mp 104-106 °C. 1H

NMR (400 MHz, CDCl3) δ 8.63 (s, 1H), 8.53 – 8.41 (m, 1H), 7.28 – 7.11

(m, 5H), 6.92 – 6.81 (m, 2H), 3.77 (s, 3H), 3.67 (s, 3H), 3.06 – 2.88 (m,

2H), 1.92 – 1.72 (m, 3H), 1.67 – 1.42 (m, 6H), 1.23 – 1.04 (m, 2H). 13C NMR (100 MHz, CDCl3)

δ 157.1, 152.6, 147.4, 146.8, 137.3, 125.9, 122.3, 121.8 (2C), 121.5, 114.9, 114.3 (2C), 111.0,

108.8, 55.5, 39.8, 36.6, 32.6 (2C), 29.7, 25.2 (2C), 23.9. IR (thin film): max = 3049, 2946,

1614, 1535, 1469, 1326, 1126, 832 cm-1. HRMS (ESI): calculated for C24H28N2O [M+ H]+:

361.2272; found 361.2274.

(E)-1-(2-(2-Cyclohexylethyl)-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine

(3ap)

The general procedure (c) was applied to (E)-N-(4-methoxyphenyl)-

1-(1-methyl-1H-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol,

1.0 eq.) and vinylcyclohexane (2p, 110.0 mg, 1.00 mmol, 2.0 eq.).

S35

Silica gel chromatography (eluent pentane/EtOAc 90/10) afforded the title compound (3ap)

as a yellow solid (170 mg, 91 %). mp 105-107 °C. 1H NMR (400 MHz, CDCl3) δ 8.60 (s, 1H),

8.44 (ddd, J = 6.7, 3.4, 2.0 Hz, 1H), 7.21 – 7.10 (m, 5H), 6.87 – 6.83 (m, 2H), 3.74 (s, 3H), 3.59

(s, 3H), 2.97 – 2.87 (m, 2H), 1.77 – 1.54 (m, 4H), 1.43 (ddd, J = 10.9, 8.2, 6.2 Hz, 2H), 1.35 –

1.02 (m, 5H), 0.97 – 0.82 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 157.1, 152.6, 147.4, 147.0,

137.3, 125.9, 122.3, 121.8 (3C), 121.5, 114.3 (2C), 110.9, 108.8, 55.5, 37.8, 37.6, 33.2 (2C),

29.6, 26.5, 26.2 (2C), 22.1. IR (thin film): max = 2995, 2921, 1594, 1469, 1410, 1290, 1004,

775 cm-1. HRMS (ESI): calculated for C25H30N2O [M+ H]+: 375.2431; found 375.2425.

2-(2-(Cyclohex-3-en-1-yl)ethyl)-1-methyl-1H-indole-3-carbaldehyde

(3aq)

A modified version procedure (c) was applied to (E)-N-(4-

methoxyphenyl)-1-(1-methyl-1H-indol-3-yl)methanimine (1a, 132 mg,

0.50 mmol, 1.0 eq.) and 4-vinylcyclohex-1-ene (2q, 108.0 mg, 1.00

mmol, 2.0 eq.). After the reaction the resulting mixture was quenched with 3M HCl (1.0 Ml).

The resulting mixture was then stirred at room temperature for 1 h, and then extracted with

ethyl acetate (3 x 10 mL). The combined organic layer was dried over MgSO4 and

concentrated under reduced pressure. Silica gel chromatography (eluent pentane/EtOAc

90/10) afforded the title compound (3aq) as an orange oil (100.1 mg, 75 %). 1H NMR (400

MHz, CDCl3) δ 10.11 (s, 1H), 8.23 – 8.16 (m, 1H), 7.28 – 7.17 (m, 3H), 5.73 – 5.52 (m, 2H),

3.66 (d, J = 1.2 Hz, 3H), 3.06 (m, 2H), 2.23 – 2.10 (m, 1H), 2.05 – 1.90 (m, 2H), 1.86 – 1.44 (m,

4H), 1.34 – 1.16 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 183.9, 152.0, 137.0, 130.3, 128.4,

127.1, 125.8, 125.7, 123.1 (2C), 122.8 (2C), 120.9, 113.6, 109.3 (2C), 36.9, 36.6, 35.0, 33.5,

31.6, 29.7, 28.7, 28.6, 25.2, 24.9, 21.9, 21.3. IR (thin film): max = 3019, 2919, 1648, 1526,

1451, 1078, 794 cm-1 HRMS (ESI): calculated for C18H22NO [M+ H]+: 268.1696; found

268.1702

Note: Increased number of carbons due to double bond migration in the cyclohexene moiety

S36

(E)-1-(2-(3-Cyclohexylpropyl)-1-methyl-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3ar)

The general procedure (C) was applied to (E)-N-(4-methoxyphenyl)-1-(1-

methyl-1H-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0 eq.) and

allylcyclohexane (2r, 124.0 mg, 1.00 mmol, 2.0 eq.). Silica gel


compound (3ar) as a yellow oil (117 mg, 61 %). 1H NMR (400 MHz, CDCl3) δ

8.62 (s, 1H), 8.49 – 8.43 (m, 1H), 7.28 – 7.09 (m, 5H), 6.89 – 6.83 (m, 2H), 3.76 (s, 3H), 3.65

(s, 3H), 2.97 – 2.89 (m, 2H), 1.66 – 1.44 (m, 9H), 1.30 – 0.99 (m, 4H), 0.86 – 0.72 (m, 2H). 13C

NMR (100 MHz, CDCl3) δ 157.1, 152.8, 147.4, 146.6, 137.3, 125.9, 122.3, 121.9, 121.8 (2C),

121.5, 114.3 (2C), 111.2, 108.8, 55.5, 37.4, 37.1, 33.3 (2C), 29.7, 27.4, 26.6, 26.3 (2C), 24.8.

IR (thin film): max = 3051, 2921, 1614, 1535, 1500, 1290, 1127, 829 cm-1. HRMS (ESI):

calculated for C26H32N2O [M+ H]+: 388.2598; found 388.2587.

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-(2-(trimethylsilyl)ethyl)-1H-indol-3-

yl)methanimine (3as)

The general procedure (C) was applied to (E)-N-(4-methoxyphenyl)-

1-(1-methyl-1H-indol-3-yl)methanimine (1a, 132 mg, 0.50 mmol, 1.0

eq.) and trimethylvinylsilane (1s, 60 mg, 0.6 mmol, 1.2 eq.). Silica gel


compound (3as) as a yellow solid (180 mg, 99 %). mp 119-121 °C. 1H

NMR (400 MHz, CDCl3) δ 8.60 (s, 1H), 8.48 – 8.30 (m, 1H), 7.15 (m,

5H), 6.84 (d, J = 8.3 Hz, 2H), 3.73 (s, 3H), 3.61 (s, 3H), 2.96 – 2.86 (m, 2H), 0.85 – 0.72 (m,

2H), 0.00 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 158.9, 154.2, 150.7, 149.2, 139.0, 127.9,

124.1, 123.6 (2C), 123.4, 123.3, 116.1 (2C), 111.7, 110.6, 57.3, 31.4, 20.8, 19.6, 0.0 (3C). IR

(thin film): max = 2949, 1612, 1470, 1240, 939, 797 cm-1. HRMS (ESI): calculated for

C22H29N2OSi [M+ H]+: 365.2033; found 365.2044.

S37

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-(2-(triphenylsilyl)ethyl)-

1H-indol-3-yl)methanimine (3at)

The general procedure (c) was applied to (E)-N-(4-


mg, 0.50 mmol, 1.0 eq.) and triphenylvinylsilane (2t, 171 mg, 0.6

mmol, 1.2 eq.). Silica gel chromatography (eluent pentane/EtOAc

85/15) afforded the title compound (3at) as a yellow foam (226

mg, 82 %). 1H NMR (400 MHz, CDCl3) δ 8.58 (s, 1H), 8.44 (ddt, J = 6.0, 3.7, 1.9 Hz, 1H), 7.68 –

7.57 (m, 7H), 7.50 – 7.32 (m, 11H), 7.16 – 7.09 (m, 2H), 6.98 – 6.90 (m, 2H), 3.87 (s, 3H), 3.57

(s, 3H), 3.21 – 3.12 (m, 2H), 1.79 – 1.70 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 157.1, 152.2,

137.2, 135.9, 135.5 (6C), 134.9, 134.1, 129.9, 129.8 (2C), 128.2, 128.1 (6C), 127.9, 126.1,

122.3, 121.9 (2C), 121.5, 121.4, 114.2 (2C), 110.0, 108.8, 55.6, 29.4, 19.2, 14.6. IR (thin film):

max = 3067, 3011, 1614, 1500, 1290, 1110, 741, 700 cm-1. HRMS (ESI): calculated for

C37H34N2OSi [M+ H]+: 551.2535; found 551.2513.

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2-(2-(triethoxysilyl)ethyl)-1H-indol-3-

yl)methanimine (3au)



mg, 0.50 mmol, 1.0 eq.) and trimethoxyvinylsilane (2u, 114 mg,


pentane/EtOAc 90/10) afforded the title compound (3au) as a

yellow oil (166 mg, 73%). 1H NMR (400 MHz, CDCl3) δ 8.67 (s, 1H),

8.43 (m, 1H), 7.26 – 7.12 (m, 5H), 6.88 – 6.83 (m, 2H), 3.80 – 3.73 (m, 9H), 3.67 (s, 3H), 3.12

– 3.03 (m, 2H), 1.15 (t, J = 7.0 Hz, 9H), 0.96 – 0.89 (m, 2H). 13C NMR (100 MHz, CDCl3) δ

157.1, 152.6, 148.3, 147.4, 137.2, 126.0, 122.3, 121.8 (2C), 121.7, 121.5, 119.0, 114.2 (2C),

110.2, 108.8, 58.6 (2C), 55.5, 29.6, 18.3 (3C), 17.9, 11.7. IR (thin film): max = 2973, 2926,

1615, 1501, 1440, 1243, 1102, 781 cm-1. HRMS (ESI): calculated for C25H35N2O4Si [M+ H]+:

455.2379; found 455.2361.

S38

(E)-1-(1,7-Dimethyl-2-(2-(trimethylsilyl)ethyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3cs)

The general procedure (C) was applied to (E)-1-(1,7-dimethyl-1H-

indol-3-yl)-N-(4-methoxyphenyl)methanimine (1c, 139 mg, 0.50

mmol, 1.0 eq.) and trimethylvinylsilane (2s, 60 mg, 0.6 mmol, 1.2


afforded the title compound (3cs) as a yellow oil (135 mg, 71 %). 1H

NMR (400 MHz, CDCl3) δ 8.70 (s, 1H), 8.42 – 8.33 (m, 1H), 7.25 –

7.19 (m, 2H), 7.11 (t, J = 7.5 Hz, 1H), 6.99 – 6.91 (m, 3H), 3.96 (s,

3H), 3.84 (s, 3H), 3.06 – 2.95 (m, 2H), 2.79 (s, 3H), 0.94 – 0.82 (m, 2H), 0.12 (s, 9H). 13C NMR

(100 MHz, CDCl3) δ 158.9, 154.3, 151.1, 149.2, 137.8, 128.8, 127.4, 123.6 (2C), 123.2, 122.3,

121.3, 116.1 (2C), 111.5, 57.3, 34.5, 22.3, 20.7, 19.4, 0.0 (3C). IR (thin film): max = 2950,

1614, 1501, 1242, 1071, 859, 749 cm-1. HRMS (ESI): calculated for C23H31N2OSi [M+ H]+:

379.2200; found 379.2215.

Methyl (E)-3-(((4-methoxyphenyl)imino)methyl)-1-methyl-2-(2-(trimethylsilyl)ethyl)-1H-

indole-6-carboxylate (3fs)


methoxyphenyl)imino)methyl)-1-methyl-1H-indole-6-carboxylate

(1f, 162 mg, 0.50 mmol, 1.0 eq.) and trimethylvinylsilane (2s, 60 mg,


pentane/EtOAc 85/15) afforded the title compound (3fs) as a

yellow oil (208 mg, 99 %). 1H NMR (400 MHz, CDCl3) δ 8.67 (s, 1H),

8.47 (dd, J = 8.4, 0.7 Hz, 1H), 8.04 (dd, J = 1.5, 0.7 Hz, 1H), 7.93 (dd, J

= 8.3, 1.5 Hz, 1H), 7.25 – 7.18 (m, 2H), 6.98 – 6.90 (m, 2H), 3.96 (s, 3H), 3.84 (s, 3H), 3.73 (s,

3H), 3.09 – 2.93 (m, 2H), 0.92 – 0.83 (m, 2H), 0.11 (s, 9H). 13C NMR (100 MHz, CDCl3) δ

169.9, 159.2, 153.6, 153.5, 148.7, 138.5, 131.7, 125.5, 124.4, 123.6 (2C), 122.8, 116.2 (2C),

112.9, 112.0, 57.4, 53.8, 31.5, 21.0, 19.4, -0.0 (3C). IR (thin film): max = 2954, 1702, 1554,

1433, 1239, 850 cm-1. HRMS (ESI): calculated for C23H31N2OSi [M+ H]+: 423.2098; found

423.2099.

S39

(E)-1-(5-Isocyano-1-methyl-2-(2-(trimethylsilyl)ethyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3gs)

The general procedure (C) was applied to (E)-1-(5-isocyano-1-methyl-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (1g, 144 mg, 0.50 mmol, 1.0 eq.) and

trimethylvinylsilane (2s, 0.60 mg, 0.6 mmol, 1.2 eq.). Silica gel


compound (3gs) as a yellow oil (156 mg, 80 %). 1H NMR (400 MHz,

CDCl3) δ 8.80 (dd, J = 1.7, 0.7 Hz, 1H), 8.55 (s, 1H), 7.37 (dd, J = 8.5,

1.6 Hz, 1H), 7.22 (dd, J = 8.5, 0.7 Hz, 1H), 7.17 – 7.09 (m, 2H), 6.88 –

6.80 (m, 2H), 3.74 (s, 3H), 3.63 (s, 3H), 2.95 – 2.83 (m, 2H), 0.81 –

0.71 (m, 2H), -0.00 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 159.5, 152.9, 152.4, 148.2, 140.7,

129.3, 127.7, 127.3, 123.7 (2C), 122.6, 116.3 (2C), 112.4, 111.4, 106.2, 57.4, 31.7, 20.9, 19.7,

0.0 (3C). IR (thin film): max = 2950, 2219, 1615, 1501, 1244, 1038, 859 cm-1. HRMS (ESI):

calculated for C23H28N3OSi [M+ H]+: 390.1996; found 390.2003.

(E)-1-(5-Fluoro-1-methyl-2-(2-(trimethylsilyl)ethyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3hs)

The general procedure (c) was applied to (E)-1-(5-fluoro-1-methyl-

1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1h, 141 mg, 0.50

mmol, 1.0 eq.) and trimethylvinylsilane (2s, 0.6 mg, 0.6 mmol, 1.2


afforded the title compound (3hs) as a yellow solid (180 mg, 99 %).

mp 122-124 °C 1H NMR (400 MHz, CDCl3) δ 8.55 (s, 1H), 8.35 (ddd, J

= 8.6, 5.7, 0.6 Hz, 1H), 7.13 – 7.07 (m, 2H), 6.94 – 6.81 (m, 4H), 3.74 (s, 3H), 3.55 (s, 3H), 2.91

– 2.81 (m, 2H), 0.84 – 0.70 (m, 2H), -0.00 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 161.9(d, J =

238.7 Hz), 159.1, 153.9, 151.1 (d, J = 2.8 Hz), 148.9, 139.4 (d, J = 11.8 Hz), 124.7 (d, J = 9.7

Hz), 124.2, 123.6 (2C), 116.2 (2C), 111.9, 111.4 (d, J = 23.3 Hz), 97.5 (d, J = 26.4 Hz), 57.4,

31.6, 20.7, 19.7, 0.0 (3C). 19F NMR (376 MHz, CDCl3) δ -119.9. IR (thin film): max = 2950,

S40

1615, 1501, 1290, 1039, 829 cm-1. HRMS (ESI): calculated for C22H28N2OSiF [M+ H]+:

383.1949; found 383.1964.

(E)-1-(6-Chloro-1-methyl-2-(2-(trimethylsilyl)ethyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3is)

The general procedure (C) was applied to (E)-1-(6-chloro-1-methyl-

1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (1i, 149 mg, 0.50

mmol, 1.0 eq.) and trimethylvinylsilane (2s, 0.6 mg, 0.6 mmol, 1.2


afforded the title compound (3is) as a yellow oil (109 mg, 55 %). 1H

NMR (400 MHz, CDCl3) δ 8.68 (s, 1H), 8.44 (dd, J = 8.4, 0.5 Hz, 1H),

7.31 (dd, J = 1.8, 0.5 Hz, 1H), 7.25 – 7.20 (m, 3H), 6.97 (d, J = 8.8 Hz, 2H), 3.86 (s, 3H), 3.70 (s,

3H), 3.05 – 2.96 (m, 2H), 0.97 – 0.85 (m, 2H), 0.15 – 0.08 (m, 9H). 13C NMR (100 MHz, CDCl3)

δ 157.2, 151.9, 149.3, 147.0, 137.7, 128.2, 124.5, 122.7, 121.9, 121.7 (2C), 114.3 (2C), 110.0,

109.0, 55.5, 29.6, 18.9, 17.8, -1.8 (3C). IR (thin film): max = 2950, 1615, 1568, 1377, 1104,

912 cm-1. HRMS (ESI): calculated for C22H28N2OSiCl [M+ H]+: 399.1654; found 399.1668.

General procedure (D): Cobalt catalysed intramolecular hydroarylation of alkenes:

To a sealed tube under argon were added Co(PMe3)4 (1 mol %), and imine (0.5mmol).

Degassed toluene (1 ml) was added and the resulting solution was heated at 110 °C for 1 h

in the microwave (absorption level normal). The reaction mixture was then filtered through

a plug of celite washing with ethyl acetate (3 x 10 ml). The crude product was purified by

silica chromatography to yield the desired product.

S41

(E)-N-(4-Methoxyphenyl)-1-(1-methyl-2,3-dihydro-1H-pyrrolo[1,2-a]indol-9-

yl)methanimine (5a)

The general procedure (D) was applied to (E)-1-(1-(but-3-en-1-

yl)-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (4a, 152

mg, 0.50 mmol, 1.0 eq.). Silica gel chromatography (eluent

pentane/EtOAc 90/10) afforded the title compound (5a) as a

yellow oil (189 mg, 95 %). 1H NMR (400 MHz, CDCl3) δ 8.75 (s,

1H), 8.56 – 8.43 (m, 1H), 7.34 – 7.17 (m, 5H), 7.03 – 6.90 (m, 2H), 4.19 (m, 1H), 4.07 (m, 1H),

3.87 (s, 3H), 3.70 (m, 1H), 2.89 (m, 1H), 2.35 – 2.24 (m, 1H), 1.54 (d, J = 7.0 Hz, 3H). 13C NMR

(100 MHz, CDCl3) δ 157.1, 154.1, 152.1, 147.3, 132.9, 130.5, 122.1, 122.0, 121.8 (2C), 121.3,

114.3 (2C), 109.6, 106.8, 55.5, 43.3, 36.0, 32.7, 20.1. IR (thin film): max = 3050, 1600, 1565,


305.1657.

1-(1-Methyl-2,3-dihydro-1H-pyrrolo[1,2-a]indol-9-yl)ethan-1-

one (5b)

A modified version of general procedure (D) was applied to

(E)-1-(1-(but-3-en-1-yl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)ethan-1-imine (4b, 160 mg, 0.50 mmol, 1.0

eq.). After the reaction the resulting mixture was quenched with 3M HCl (1.0 ml). The

resulting mixture was then stirred at room temperature for 1 h, and then extracted with

ethyl acetate (3 x 10 mL). The combined organic layer was dried over MgSO4 and

concentrated under reduced pressure. Silica gel chromatography (eluent pentane/EtOAc

80/20) afforded the title compound (5b) as a yellow oil (91 mg, 85 %). 1H NMR (400 MHz,

CDCl3) δ 8.25 – 8.10 (m, 1H), 7.40 – 7.17 (m, 3H), 4.16 (m, 2H), 3.80 (m, 1H), 2.89 (m, 1H),

2.63 (s, 3H), 2.40 – 2.29 (m, 1H), 1.44 (d, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 156.8,

132.4, 130.5, 122.2, 122.1 (2C), 121.7, 109.9 (2C), 42.9, 35.2, 34.1, 29.7, 19.1. IR (thin film):

max = 3050, 1636, 1571, 1459, 841 cm-1. HRMS (ESI): calculated for C14H16NO [M+ H]+:

214.1190; found 214.1189.

S42

(E)-N-(4-Methoxyphenyl)-1-(1-propyl-2,3-dihydro-1H-pyrrolo[1,2-a]indol-9-

yl)methanimine (5c)

The general procedure (D) was applied to (E)-1-(1-((Z)-hex-3-

en-1-yl)-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (4c,

166 mg, 0.50 mmol, 1.0 eq.). Silica gel chromatography

(eluent pentane/EtOAc 90/10) afforded the title compound

(5c) as a yellow oil (164 mg, 99 %). 1H NMR (400 MHz, CDCl3)

δ 8.60 (s, 1H), 8.42 – 8.31 (m, 1H), 7.18 – 7.10 (m, 5H), 6.91 – 6.79 (m, 2H), 4.10 – 3.94 (m,

2H), 3.75 (s, 3H), 3.56 – 3.46 (m, 1H), 2.80 – 2.67 (m, 1H), 2.34 – 2.25 (m, 1H), 1.93 – 1.82

(m, 1H), 1.59 (m, 1H), 1.38 (m, 2H), 0.89 (t, J = 7.3 Hz, 3H).13C NMR (100 MHz, CDCl3) δ

157.0, 153.3, 152.3, 147.3, 133.0, 130.5, 122.2, 122.0, 121.7 (2C), 121.3, 114.3 (2C), 109.5,

107.0, 55.5, 43.4, 37.7, 36.7, 33.5, 20.5, 14.1. IR (thin film): max = 2953, 1615, 1459, 1329,


333.1968.

(E)-1-(1,2-Dimethyl-2,3-dihydro-1H-pyrrolo[1,2-a]indol-9-yl)-N-(4-

methoxyphenyl)methanimine (5d)

The general procedure (D) was applied to (E)-N-(4-

methoxyphenyl)-1-(1-(2-methylbut-3-en-1-yl)-1H-indol-3-

yl)methanimine (4c, 166 mg, 0.50 mmol, 1.0 eq.). Silica gel

chromatography (eluent pentane/EtOAc 90/10) afforded the

title compound (5d) as a yellow oil (157 mg, 99 %) and as a

mixture of diasteroisomers 86/14 as determined by 1H NMR.

The characteristic peaks for the minor diasteroisomer are as follows: δ 8.72 (s, 1H), 8.46 –

8.42 (m, 1H), 4.23 (dd, J = 10.2, 7.6 Hz, 1H), 1.26 (d, J = 7.1 Hz, 3H).

major diasteroisomer 1H NMR (400 MHz, CDCl3) δ 8.76 (s, 1H), 8.52 – 8.47 (m, 1H), 7.31 –

7.22 (m, 5H), 7.01 – 6.93 (m, 2H), 4.33 (dd, J = 10.3, 7.6 Hz, 1H), 3.87 (s, 3H), 3.70 – 3.62 (m,

S43

1H), 3.25 – 3.15 (m, 1H), 2.67 (m, 1H), 1.57 (d, J = 6.9 Hz, 3H), 1.34 (d, J = 7.1, 3H). 13C NMR

(100 MHz, CDCl3) δ 157.0, 153.5, 152.1, 147.3, 133.0, 130.2, 122.3, 122.1, 121.7 (2C), 121.3,

114.3 (2C), 109.5, 107.3, 55.5, 50.6, 45.2, 41.1, 18.4, 18.1. IR (thin film): max = 2960, 1614,


found 319.1810.

(E)-1-(7-Methoxy-1-methyl-2,3-dihydro-1H-pyrrolo[1,2-a]indol-9-yl)-N-(4-

methoxyphenyl)methanimine (5e)

The general procedure (D) was applied to methyl (E)-1-(1-

(but-3-en-1-yl)-5-methoxy-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (4e, 168 mg, 0.50 mmol, 1.0


afforded the title compound (5e) as a yellow oil (166 mg, 99

%). 1H NMR (400 MHz, CDCl3) δ 8.60 (s, 1H), 7.92 (d, J = 2.5 Hz, 1H), 7.17 – 7.10 (m, 2H), 7.05

(d, J = 8.7 Hz, 1H), 6.89 – 6.81 (m, 2H), 6.78 (dd, J = 8.7, 2.5 Hz, 1H), 4.06 (m, 1H), 3.95 (m,

1H), 3.83 (s, 3H), 3.75 (s, 3H), 3.58 (m, 1H), 2.78 (m, 1H), 2.17 (m, 1H), 1.41 (d, J = 7.0 Hz,

3H). 13C NMR (100 MHz, CDCl3) δ 157.0, 155.6, 154.6, 152.1, 147.4, 131.1, 127.9, 121.8 (2C),

114.3 (2C), 111.9, 110.3, 106.7, 104.6, 55.9, 55.5, 43.5, 36.0, 32.8, 20.2. IR (thin film): max =

2959, 1615, 1541, 1287, 1134, 940 cm-1. HRMS (ESI): calculated for C21H23N2O2 [M+

H]+:335.1754; found 335,1751.

Methyl (E)-9-(((4-methoxyphenyl)imino)methyl)-1-methyl-2,3-dihydro-1H-pyrrolo[1,2-

a]indole-6-carboxylate (5f)

The general procedure (d) was applied methyl to (E)-1-(but-3-

en-1-yl)-3-(((4-methoxyphenyl)imino)methyl)-1H-indole-6-

carboxylate (4f, 182 mg, 0.50 mmol, 1.0 eq.). Silica gel

chromatography (eluent pentane/EtOAc 80/20) afforded the

title compound (5f) as a yellow oil (180 mg, 99 %). 1H NMR

(400 MHz, CDCl3) δ 8.63 (s, 1H), 8.33 (dd, J = 8.4, 0.7 Hz, 1H),

7.93 (dd, J = 1.5, 0.7 Hz, 1H), 7.84 (dd, J = 8.4, 1.5 Hz, 1H), 7.16 – 7.06 (m, 2H), 6.95 – 6.79

S44

(m, 2H), 4.16 (dd, J = 8.1, 6.2 Hz, 1H), 4.11 – 4.02 (m, 1H), 3.88 (s, 3H), 3.76 (s, 3H), 3.70 –

3.62 (m, 1H), 2.85 (m, 1H), 2.30 – 2.19 (m, 1H), 1.45 (d, J = 7.0 Hz, 3H). 13C NMR (100 MHz,

CDCl3) δ 167.9, 157.3, 156.7, 151.4, 146.8, 134.2, 132.2, 123.6, 122.4, 121.7 (2C), 121.5,

114.3 (2C), 111.8, 107.2, 55.5, 51.9, 43.6, 35.9, 32.9, 19.8. IR (thin film): max = 2951, 1710,

1617, 1559, 1295, 772 cm-1. HRMS (ESI): calculated for C22H22N2O3 [M+ H]+:363.1703; found

363.1691.

S45

VI. NMR Spectra for new compounds: (E)-1-(2-((Z)-1,2-diphenylvinyl)-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine (3aa)

S46

(E)-N-(4-methoxyphenyl)-1-(1-methyl-2-((Z)-1-phenyl-2-(trimethylsilyl)vinyl)-1H-indol-3-

yl)methanimine (3ab)

S47

(Z)-1-methyl-2-(1-phenylhex-1-en-1-yl)-1H-indole-3-carbaldehyde (3ac)

S48

(E)-N-(4-methoxyphenyl)-1-(1-methyl-2-((Z)-1-(pyridin-3-yl)-2-(trimethylsilyl)vinyl)-1H-

indol-3-yl)methanimine (3ad)

S49


yl)methanimine (3ae)

S50


yl)methanimine (3af)

S51

(E)-N-(4-methoxyphenyl)-1-(1-methyl-2-(1-phenylethyl)-1H-indol-3-yl)methanimine (3ag)

S52

(E)-N-(4-methoxyphenyl)-1-(1-methyl-2-(1-(p-tolyl)ethyl)-1H-indol-3-yl)methanimine

(3ah)

S53

(E)-N-(4-methoxyphenyl)-1-(2-(1-(3-methoxyphenyl)ethyl)-1-methyl-1H-indol-3-yl)methanimine (3ai)

S54

(E)-N-(4-methoxyphenyl)-1-(2-(1-(2-methoxyphenyl)ethyl)-1-methyl-1H-indol-3-

yl)methanimine(3aj)

Linear Product

S55

(E)-1-(2-(1-(4-fluorophenyl)ethyl)-1-methyl-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3ak)

S57

(E)-N-(4-methoxyphenyl)-1-(1-methyl-2-(1-(naphthalen-2-yl)ethyl)-1H-indol-3-

yl)methanimine(3al)

S58

(E)-N-(4-methoxyphenyl)-1-(1-methyl-2-(1-phenylpropyl)-1H-indol-3-yl)methanimine

(3am)

S59

(E)-N-(4-methoxyphenyl)-1-(1-methyl-2-(1-(pyridin-4-yl)ethyl)-1H-indol-3-yl)methanimine (3an)

S60

(E)-1-(5-(benzyloxy)-1-methyl-2-(1-phenylethyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3bg)

S61

(E)-1-(1,7-dimethyl-2-(1-phenylethyl)-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine

(3cg)

S62

(E)-1-(5-methoxy-1-methyl-2-(1-phenylethyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3dg)

S63

(E)-1-(5-(benzyloxy)-1-methyl-2-(1-phenylethyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3eg)

S64

Methyl (E)-3-(((4-methoxyphenyl)imino)methyl)-1-methyl-2-(1-phenylethyl)-1H-indole-6-

carboxylate (3fg)

S65

(E)-3-(((4-methoxyphenyl)imino)methyl)-1-methyl-2-(1-phenylethyl)-1H-indole-5-

carbonitrile (3gg)

S66

(E)-1-(5-fluoro-1-methyl-2-(1-phenylethyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3hg)

S68

(E)-1-(2-(2-cyclopentylethyl)-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine

(3ao)

S69

(E)-1-(2-(2-cyclohexylethyl)-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine

(3ap)

S70

2-(2-(cyclohex-3-en-1-yl)ethyl)-1-methyl-1H-indole-3-carbaldehyde (3aq)

S71

(E)-1-(2-(3-cyclohexylpropyl)-1-methyl-1H-indol-3-yl)-N-(4-methoxyphenyl)methanimine

(3ar)

S72

(E)-N-(4-methoxyphenyl)-1-(1-methyl-2-(2-(trimethylsilyl)ethyl)-1H-indol-3-

yl)methanimine (3as)

S73

(E)-N-(4-methoxyphenyl)-1-(1-methyl-2-(2-(triphenylsilyl)ethyl)-1H-indol-3-

yl)methanimine (3at)

S74

(E)-N-(4-methoxyphenyl)-1-(1-methyl-2-(2-(trimethylsilyl)ethyl)-1H-indol-3-

yl)methanimine (3au)

S75

(E)-1-(1,7-dimethyl-2-((trimethylsilyl)methyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine(3cs)

S76

Methyl (E)-3-(((4-methoxyphenyl)imino)methyl)-1-methyl-2-(2-(trimethylsilyl)ethyl)-1H-

indole-6-carboxylate (3fs)

S77

(E)-1-(5-isocyano-1-methyl-2-(2-(trimethylsilyl)ethyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine(3gs)

S78

(E)-1-(5-fluoro-1-methyl-2-(2-(trimethylsilyl)ethyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3hs)

S80

(E)-1-(6-chloro-1-methyl-2-(2-(trimethylsilyl)ethyl)-1H-indol-3-yl)-N-(4-

methoxyphenyl)methanimine (3is)

S81

(E)-N-(4-methoxyphenyl)-1-(1-methyl-2,3-dihydro-1H-pyrrolo[1,2-a]indol-9-

yl)methanimine(5a)

S82

1-(1-methyl-2,3-dihydro-1H-pyrrolo[1,2-a]indol-9-yl)ethan-1-one

(5b)

S83

(E)-N-(4-methoxyphenyl)-1-(1-propyl-2,3-dihydro-1H-pyrrolo[1,2-a]indol-9-

yl)methanimine (5c)

S84

(E)-1-(7-methoxy-1-methyl-2,3-dihydro-1H-pyrrolo[1,2-a]indol-9-yl)-N-(4-

methoxyphenyl)methanimine (5e)

S85

Methyl (E)-9-(((4-methoxyphenyl)imino)methyl)-1-methyl-2,3-dihydro-1H-pyrrolo[1,2-

a]indole-6-carboxylate (5f)

S86

VII. References:

1. D. D. Perrin, W. L. F. Armarego, Purification of Laboratory Chemicals ; 3rd ed.,

Pergamon Press, Oxford, 1988.

2. W.C. Still, M. Kahn, A. J. Mitra, J. Org. Chem. 1978, 43, 2923.

3. P.-S. Lee. N. Yoshikai, Org. Lett. 2015, 17, 22−25.

4. Z. Ding, N. Yoshikai, Angew. Chem., Int. Ed. 2013, 52, 8574−8578.

5. (a) H. F. Klein, Angew. Chem., Int. Ed. Engl., 1971, 10, 343 (b) H. F. Klein, H. H. Karsch.

Chem. Ber., 1975, 108, 944.

6. S. Ventre, C. Simon, F. Rekhroukh, M. Malacria, M. Amatore, C. Aubert, M. Petit. Chem.

Eur. J. 2013, 19, 5830-5835.

7. B. J. Fallon, J.-B. Derat, E. Derat, M. Amatore, C. Aubert, M. Petit, ACS Catal. 2015, 5,

7493−7497

institut parisien de chimie moléculaire, umr 8232, …...s7 ii. dft calculations xyz coordinates ch...

Documents