S1

Asymmetric Synthesis of Cyclopentanones through Dual Lewis Acid-Catalysed [3 + 2]-Cycloaddition of Donor-Acceptor Cyclopropanes

with Ketenes

Mukulesh Mondal,a Manashi Panda,a Nicholas W. Davis,a Vickie McKee,b,c and Nessan J. Kerriganb,*

a Department of Chemistry, Oakland University, 2200 N. Squirrel Road, Rochester, MI 48309-4477, USA.

b School of Chemical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland.

c Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark.

NMR and GC/HPLC spectra

Table of Contents:

GC of (±)-1a S4

GC of 1a S5

GC of (±)-1b S6

GC of (S)-1b S7

GC of (R)-1b S8

GC of (±)-1c S9

GC of (S)-1c S10

GC of (R)-1c S11

GC of (±)-1e S12

GC of (S)-1e S13

GC of (R)-1e S14

HPLC of (±)-4a S15

HPLC of (–)-4a S16

1H & 13C NMR of (–)-4a S17

HPLC of (±)-4b S18

HPLC of (+)-4b S19

1H & 13C NMR of (+)-4b S20

HPLC of (±)-4c S21

HPLC of (–)-4c S22

HPLC of (+)-4d S23

1H & 13C NMR of (–)-4c S24

1H & 13C NMR of (+)-4d S25

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2019

S2

1H & 13C NMR of (±)-4e S26

HPLC of (±)-4f S27

HPLC of (–)-4f S28

HPLC of (+)-4g S29

1H & 13C NMR of (–)-4f S30

1H & 13C NMR of (+)-4g S31

HPLC of (±)-4h S32

HPLC of (–)-4h S33

HPLC of (+)-4i S34

1H & 13C NMR of (–)-4h S35

1H & 13C NMR of (+)-4i S36

HPLC of (±)-4j S37

HPLC of (–)-4j S38

HPLC of (+)-4k S39

1H & 13C NMR of (–)-4j S40

1H & 13C NMR of (+)-4k S41

HPLC of (±)-4l S42

HPLC of (–)-4l S43

HPLC of (+)-4m S44

1H & 13C NMR of (–)-4l S45

1H & 13C NMR of (+)-4m S46

1H & 13C NMR of (–)-4n S47

1H & 13C NMR of (+)-4o S48

HPLC of (±)-4p S49

HPLC of (–)-4p S50

HPLC of (+)-4q S51

1H & 13C NMR of (–)-4p S52

1H & 13C NMR of (+)-4q S53

HPLC of (±)-4r S54

HPLC of (–)-4r S55

HPLC of (+)-4s S56

1H & 13C NMR of (–)-4r S57

1H & 13C NMR of (+)-4s S58

HPLC of (±)-4t S59

S3

HPLC of (–)-4t S60

HPLC of (+)-4v S61

HPLC of (±)-4u S62

HPLC of (+)-4u S63

HPLC of (–)-4w S64

1H & 13C NMR of (–)-4t S65

1H & 13C NMR of (+)-4u S66

1H & 13C NMR of (+)-4v S67

1H & 13C NMR of (–)-4w S68

1H & 13C NMR of (+)-5u S69

S4

(±)-1a GC Trace

S5

(S)-1a GC Trace

S6

(±)-1b GC Trace

S7

(S)-1b GC Trace

S8

(R)-1b GC Trace

S9

(±)-1c GC Trace

S10

(S)-1c GC Trace

S11

(R)-1c GC Trace

S12

(±)-1e HPLC Trace

S13

(S)-1e HPLC Trace

S14

(R)-1e HPLC Trace

S15

(±)-4a HPLC Trace

S16

(–)-4a HPLC Trace

S17

(–)-4a 1H NMR

CDCl3, 400 MHz

(–)-4a 13C NMR

CDCl3, 100 MHz

S18

(±)-4b HPLC Trace

S19

(+)-4b HPLC Trace

S20

(+)-4b 1H NMR

CDCl3, 400 MHz

(+)-4b 13C NMR

CDCl3, 100 MHz

S21

(±)-4c HPLC Trace

S22

(–)-4c HPLC Trace

S23

(+)-4d HPLC Trace

S24

(–)-4c 1H NMR

CDCl3, 400 MHz

(–)-4c 13C NMR

CDCl3, 100 MHz

S25

(+)-4d 1H NMR

CDCl3, 400 MHz

(+)-4d 13C NMR

CDCl3, 100 MHz

S26

(±)-4e 1H NMR

CDCl3, 400 MHz

(±)-4e 13C NMR

CDCl3, 100 MHz

S27

(±)-4f HPLC Trace

S28

(–)-4f HPLC Trace

S29

(+)-4g HPLC Trace

S30

(–)-4f 1H NMR

CDCl3, 400 MHz

(–)-4f 13C NMR

CDCl3, 100 MHz

S31

(+)-4g 1H NMR

CDCl3, 400 MHz

(+)-4g 13C NMR

CDCl3, 100 MHz

S32

(±)-4h HPLC Trace

S33

(–)-4h HPLC Trace

S34

(+)-4i HPLC Trace

S35

(–)-4h 1H NMR

CDCl3, 400 MHz

(–)-4h 13C NMR

CDCl3, 100 MHz

S36

(+)-4i 1H NMR

CDCl3, 400 MHz

(+)-4i 13C NMR

CDCl3, 100 MHz

S37

(±)-4j HPLC Trace

S38

(–)-4j HPLC Trace

S39

(+)-4k HPLC Trace

S40

(–)-4j 1H NMR

CDCl3, 400 MHz

(–)-4j 13C NMR

CDCl3, 100 MHz

S41

(+)-4k 1H NMR

CDCl3, 400 MHz

(+)-4k 13C NMR

CDCl3, 100 MHz

S42

(±)-4l HPLC Trace

S43

(–)-4l HPLC Trace

S44

(+)-4m HPLC Trace

S45

(–)-4l 1H NMR

CDCl3, 400 MHz

(–)-4l 13C NMR

CDCl3, 100 MHz

S46

(+)-4m 1H NMR

CDCl3, 400 MHz

(+)-4m 13C NMR

CDCl3, 100 MHz

S47

(–)-4n (dr 3:1) 1H NMR

CDCl3, 400 MHz

(–)-4n (dr 3:1) 13C NMR

CDCl3, 100 MHz

S48

(+)-4o (dr 3:1) 1H NMR

CDCl3, 400 MHz

(+)-4o (dr 3:1) 13C NMR

CDCl3, 100 MHz

S49

(±)-4p HPLC Trace

S50

(–)-4p HPLC Trace

S51

(+)-4q HPLC Trace

S52

(–)-4p 1H NMR

CDCl3, 400 MHz

(–)-4p 13C NMR

CDCl3, 100 MHz

S53

(+)-4q 1H NMR

CDCl3, 400 MHz

(+)-4q 13C NMR

CDCl3, 100 MHz

S54

(±)-4r HPLC Trace

S55

(–)-4r HPLC Trace

S56

(+)-4s HPLC Trace

S57

(–)-4r 1H NMR

CDCl3, 400 MHz

(–)-4r 13C NMR

CDCl3, 100 MHz

S58

(+)-4s 1H NMR

CDCl3, 400 MHz

(+)-4s 13C NMR

CDCl3, 100 MHz

S59

(±)-4t (Major isomer) HPLC Trace

S60

(–)-4t (Major isomer) HPLC Trace

S61

(+)-4v (Major isomer) HPLC Trace

S62

(±)-4u (Minor isomer) HPLC Trace

S63

(+)-4u (Minor isomer) HPLC Trace

S64

(–)-4w (Minor isomer) HPLC Trace

S65

(–)-4t (Major isomer) 1H NMR

CDCl3, 400 MHz

(–)-4t (Major isomer) 13C NMR

CDCl3, 100 MHz

S66

(+)-4u (Minor isomer) 1H NMR

CDCl3, 400 MHz

(+)-4u (Minor isomer) 13C NMR

CDCl3, 100 MHz

S67

(+)-4v (Major isomer) 1H NMR

CDCl3, 400 MHz

(+)-4v (Major isomer) 13C NMR

CDCl3, 100 MHz

S68

(–)-4w (Minor isomer) 1H NMR

CDCl3, 400 MHz

(–)-4w (Minor isomer) 13C NMR

CDCl3, 100 MHz

S69

CDCl3, 400 MHz

CDCl3, 100 MHz