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TRANSCRIPT
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Electronic Supplementary Information
for
Visible-light-induced denitrogenative phosphorylation ofbenzotriazinones: a metal- and additive-free method foraccessing ortho-phosphorylated benzamide derivatives
Fushan Chen, Shanshan Hu, Sipei Li, Guo Tang,* and Yufen Zhao
Department of Chemistry, College of Chemistry and Chemical Engineering, and the KeyLaboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian361005, ChinaE-mail: [email protected]
Table of Contents
1. General information......................................................................................................... S22. General preparation of 1,2,3-Benzotriazin-4(3H)-one derivatives............................... S23. General procedure for photo-reaction………………………….................................... S44. Investigation for reaction mechanism…………………………………………………. S55. Luminescence quenching experiments............................................................................ S66. Cyclic voltammetry studies……………………………………………………………. S97. Characterization for all the products………………..................................................... S108. 1H, 13C and 31PNMR spectrum for all the products……............................................. S27
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2020
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1. General information.All reactions were carried out under dry argon. all reagents and solvents were obtained fromcommercial suppliers and used without further purification. 1H, 13C and 31P NMR spectra weremeasured on Bruker AV 500M spectrometers with CDCl3 as solvent and tetramethylsilane (TMS)as internal standard for 1H and 13C NMR spectra, 85% H3PO4 as external standard for 31P NMRspectra. Data are represented as follows: chemical shift, multiplicity (s = singlet, d = doublet, t =triplet, q = quartet, m = multiplet, dd = doublet of doublets, dt = doublet of triplets), couplingconstants in Hertz (Hz). The products were purified by column chromatography on silica gel300-400 mesh. The unknown products were further characterized by HRMS (FT-ICR-MS) and anelectrospray ionization source in positive-ion mode.
2. General preparation of 1,2,3-Benzotriazin-4(3H)-one derivatives.
Method A: (1a-1c, 1f-1m, 1o-1q, 1s).1
A mixture of the benzo[d][1,2,3]triazin-4(3H)-one (5.0 mmol), organoboronic acid (7.5 mmol),anhydrous Cu(OAc)2 (5.0 mmol) and Et3N (10.0 mmol) in DCE (30.0 mL) was stirred at roomtemperature till the reaction finished (monitored by TLC). The reaction mixture was filteredthrough celite. The filtrate was collected, concentrated in vacuo, and the residue was purified bychromatography on silica gel using hexane/ethyl acetate to afford the desired product.
Method B: (1d-1e, 1n, 1r, 1t, 1x).2
To a round bottom flask containing methyl anthranilate derivatives (10.0 mmol) were evacuatedand purged with argon three times. and then HCl(aq) (16.0 mL, 2 M) was added, then stirred at0 °C for 5 min. A solution of NaNO2 (11.7 mmol) in water (5.5 mL) were slowly added within 40min to the system and then stirred at 0 °C for 30 min. Then, a solution of NaOAc (38.6 mmol) inwater (12.5 mL) was slowly added within 20 min, followed by addition of corresponding anilines(15.2 mmol) at 0 °C. The resulting mixture was stirred at 0 °C for 3 h. The precipitate wascollected by filtration, washed with cold water (25.0 ml). The above triazene and morpholine (30.0mmol) was refluxed in ethanol (75.0 mL) until triazene was completely consumed. The reactionmixture was cooled to -30 °C for crystallization. The product was collected by filtration andwashed with cold ethanol to give corresponding products as white solid.
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Method C: (1u-1w, 1y,)3,4
To a stirred solution of anthranilic acid derivatives (10.0 mmol) in dichloromethane (CH2Cl2)(30.0 mL) was added EDCl·HCl (12.0 mmol), HOBt (12.0 mmol) and aniline derivatives (12.0mmol) followed by the dropwise addition of DIPEA (25.0 mmol). The reaction mixture wasallowed to stir at room temperature until the completion of reaction was monitored by TLC (24 ~36 h). After completion, the reaction mixture was diluted with ice water (90.0 mL) followed by theextraction with ethyl acetate (3*60 mL). The combined organic layer was washed with 1M HC1(100.0 mL) followed by saturated brine solution, dried over Na2SO4 and concentrated undervacuum. The obtained crude purified by silica gel column chromatograph using petroleumether/ethyl acetate as the eluent to afford the desired products.To a stirred solution of 2-amino-N-phenylbenzamide derivative (8 mmol) in MeCN (50.0 mL)
were added NaNO2 (24. 0 mmol) and I2 (8.0 mmol) at room temperature and the mixture was thenheated at 80 °C for 3 h. then the solvent was removed under vacuum and the residue was dilutedwith H2O (200 mL) and extracted with EtOAc (3x80 mL). The combined organic layer was driedover Na2SO4 and evaporated under reduced pressure. The crude residue was purified by columnchromatography over silica gel using petroleum ether/ethyl acetate (4:1, v/v) as the eluent toafford the desired product.
Method D: (1z).4
A schlenk tube containing 1,2,3-benzotriazin-4(3H)-one (10.0 mmol), K2CO3 (14.7 mmol) wereevacuated and purged with argon three times. Dry DMF (14.7 mL), alkyl bromide (16.2 mmol)were sequentially added to the system at 0 °C. Subsequently, the mixture was stirred at roomtemperature for 12 h, and then quenched with addition of water (120.0 mL), extracted with ethylacetate (3*80 mL). The combined organic layer were washed with brine and dried over MgSO4.The solvent was removed under reduced pressure and the residue was purified by flashchromatography using petroleum ether/ethyl acetate as the eluent to afford the desired products.1. K. S. Kumar, R. Adepua, S. Sandraa, D. Rambabua, G. R. Krishna, C. M. Reddy, P. Misraa andM. Pal, Bioorg. Med. Chem. Lett., 2012, 22, 1146-1150.2. a) Y. Motoshi, M. Masao, M. Tomoya and M. Masahiro, J. Am. Chem. Soc., 2010, 132, 54- 55;b) A. S. Clark, B. Deans, M. F. G. Stevens, M. J. Tisdale, R. T. Wheelhouse, B. J. Denny and J. A.Hartley, J. Med. Chem., 1995, 38, 1493-1504; c) V. H. Thorat, N. S. Upadhyay, M. Murakami andC. –H. Cheng, Adv. Synth. Catal., 2018, 360, 284-289.3. a) G. C. Senadi, V. S. Kudale and J.-J. Wang, Green Chem., 2019, 21, 979-985; b) D. S. Barak,S. Mukhopadhyay, D. J. Dahatonde and S. Batra, Tetrahedron Lett., 2019, 60, 248-251.4. T. Miura, M. Yamauchi and M. Murakami, Org. Lett., 2008, 10, 3085-3088.
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3. General procedure for photoreaction.
Organic-dye-catalyzed denitrogenative phosphorylation of benzotriazinones
A schlenk tube containing benzotriazinone derivatives (1, 0.2 mmol) and eosin Y (0.01 mmol)were evacuated and purged with argon three times. DIPEA (0.4 mmol), phosphorylation reagent (2,0.3 mmol), H2O (0.3 mL) and CH3CN (2.0 mL) were sequentially added to the system at roomtemperature. Then the system stirred at room temperature under the irradiation of 30 W blue LEDsfor 90 min (or irradiated by sunlight at 25-30 oC for 6 h). Afterwards, the solvent was removed invacuum, and residues were purified by silica gel column chromatograph using petroleumether/ethyl acetate as the eluent (2:1) to afford the desired phosphorylation products.
Gram-scale preparation of 3a and 4i
A round flask containing benzotriazinone derivatives 1a, and eosin Y (5 mol %) were evacuatedand purged with argon three times. DIPEA (2.0 equiv), phosphorylation reagent 2a (2g) (1.5 equiv)A mixture of H2O and CH3CN (0.3:2.0) were sequentially added to the system at roomtemperature. Then the system stirred at room temperature under the irradiation of 30 W blue LEDsfor 24 hours (or irradiated by sunlight at 25-30 oC for 36 h). Quenched with addition of potassiumcarbonate and water (6 mL/1 mmol) to pH = 8.5 and extracted with ethyl acetate (3*60 mL). Thecombined organic layer were removed in vacuum, dried over with MgSO4. Recrystallization usinga petroleum ether/AcOEt mixture as the solvent to afford the desired phosphorylation products.
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4. Investigation for reaction mechanism.
A schlenk tube containing benzotriazinone derivative (1a, 0.2 mmol), eosin Y (0.01 mmol) andTEMPO (1.0 mmol) were evacuated and purged with argon three times. DIPEA (0.4 mmol),phosphorylation reagent (2a, 0.3 mmol), H2O (0.3 mL) and CH3CN (2.0 mL) were sequentiallyadded to the system at room temperature. Then the system stirred at room temperature under theirradiation of 30 W blue LEDs for 90 min.
A schlenk tube containing benzotriazinone derivatives (1, 0.2 mmol), B2pin2 (4, 0.4 mmol) andeosin Y (0.01 mmol) were evacuated and purged with argon three times. DIPEA (0.4 mmol), H2O(0.3 mL) and CH3CN (2.0 mL) were sequentially added to the system at room temperature. thenthe system stirred at room temperature under the irradiation of 30 W blue LEDs for 90 min.Remove the solvent under vacuum, residues were purified by silica gel column chromatographusing petroleum ether/ethyl acetate as the eluent (4:1) to afford the desired products.
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5. Luminescence quenching experiments.
the emission spectra of a 4.3 × 10-3 M solution of eosin Y in degassed CH3CN: H2O = 20:3 excitedat 575 nm;
the emission spectra of a 4.3 × 10-3 M solution of eosin Y with various concentrations of DIPEA inin degassed CH3CN: H2O = 20:3 excited at 575 nm;
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The Stern−Volmer plot of a 4.3 × 10-3 M solution of eosin Y with various concentrations ofDIPEA in in degassed CH3CN: H2O = 20:3 excited at 575 nm;
the emission spectra of a 4.3 × 10-3 M solution of eosin Y with various concentrations of 1a indegassed anhydrous CH3CN: H2O = 20:3 excited at 575 nm;
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the emission spectra of a 4.3 × 10-3 M solution of eosin Y with various concentrations of 2a indegassed anhydrous CH3CN: H2O = 20:3 excited at 575 nm.
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6. Cyclic Voltammetry StudiesThe cyclic voltammograms were recorded in an electrolyte of Et4NPF6 (0.1 M) in the indicatedsolvent (6 mL) using a glassy carbon disk working electrode (diameter, 1 mm), a Pt wire auxiliaryelectrode and a SCE reference electrode. The scan rate was 100 mV/s.
Cyclic voltammogram of DIPEA (10 mM) in MeCN, Ep/2ox = 0.63 V.
Cyclic voltammogram of 1a (10 mM) in MeCN, Ep/2ox = 2.04 V
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7. Characterization for all the products.
Diethyl (2-(phenylcarbamoyl)phenyl)phosphonate (3a, CAS NO. 41327-48-4)
White solid; 60.6 mg, 91% yield; 1H NMR (CDCl3, 500 MHz): δ 9.15 (s, 1H), 7.91-7.86 (m, 2H),
7.72 (d, J = 7.6 Hz, 2H), 7.64 (t, J = 7.7 Hz, 1H), 7.56-7.53 (m, 1H), 7.34 (t, J = 8.0 Hz, 2H), 7.12
(t, J = 7.2 Hz, 1H), 4.17-4.12 (m, 4H), 1.28 (t, J = 7.3 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz):
δ 166.5 (d, J = 4.5 Hz), 140.4 (d, J = 10.0 Hz), 138.5, 133.0 (d, J = 2.2 Hz), 132.8 (d, J = 8.9 Hz),
130.8 (d, J = 13.2 Hz), 130.3 (d, J = 13.8 Hz), 129.2, 125.2 (d, J = 187.0 Hz), 124.7, 120.2, 63.5
(d, J = 6.7 Hz), 16.4 (d, J = 6.7 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.78; IR (film) υmax: 2979,
1605, 1679, 1601, 1543, 1441, 1322, 1230, 1142, 1104, 988, 755 cm-1; HRMS: [M+H]+ m/z calcd
for C17H21NO4P+ 334.1203, found 334.1205.
Diethyl (2-(m-tolylcarbamoyl)phenyl)phosphonate (3b, new compound)
White solid; 60.4 mg, 87% yield; 1H NMR (CDCl3, 500 MHz): δ 9.09 (s, 1H), 7.90-7.85 (m, 2H),
7.64 (d, J = 7.4 Hz, 1H), 7.55-7.51 (m, 3H), 7.23 (t, J = 7.7 Hz, 1H), 6.94 (d, J = 7.5 Hz, 1H),
4.17-4.13 (m, 4H), 2.35 (s, 3H), 1.29 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ
166.4 (d, J = 5.5 Hz), 140.5 (d, J = 10.9 Hz), 139.1, 138.4, 133.0 (d, J = 2.6 Hz), 132.7 (d, J = 8.3
Hz), 130.8 (d, J = 13.2 Hz), 130.2 (d, J = 14.3 Hz), 129.0, 125.5, 125.2 (d, J = 187.1 Hz), 120.7,
117.2, 63.4 (d, J = 6.6 Hz), 21.7, 16.4 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.87; IR
(film) υmax: 3265, 2982, 1680, 1614, 1511, 1489, 1372, 1025, 970, 780, cm-1; HRMS: [M+H]+
m/z calcd for C18H23NO4P+ 348.1359, found 348.1358.
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Diethyl (2-(o-tolylcarbamoyl)phenyl)phosphonate (3c, new compound)
White solid; 59.0 mg, 85% yield; 1H NMR (CDCl3, 500 MHz): δ 8.52 (s, 1H), 8.02 (d, J = 8.7 Hz,
1H), 7.92 (dd, J1 = 14.2 Hz, J2 = 7.6 Hz, 1H), 7.82 (t, J = 6.2 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H),
7.57-7.54 (m, 1H), 7.24 (t, J = 7.9 Hz, 1H), 7.20 (d, J = 7.5 Hz, 1H), 7.09 (t, J = 7.4 Hz, 1H),
4.17-4.13 (m, 4H), 2.31 (s, 3H), 1.30 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ
166.8 (d, J = 4.4 Hz), 140.6 (d, J = 9.9 Hz), 136.1, 132.97 (d, J = 3.3 Hz), 132.96 (d, J = 7.7 Hz),
130.7, 130.20 (d, J = 13.2 Hz), 130.17, 130.0 (d, J = 13.6 Hz), 126.8, 125.5, 125.4 (d, J = 187.1
Hz), 123.1, 63.3 (d, J = 5.5 Hz), 18.0, 16.4 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.57;
IR (film) υmax: 2983, 1679, 1532, 1488, 1453, 1312, 1024, 981, 752 cm-1; HRMS: [M+Na]+ m/z
calcd for C18H22NO4PNa+ 370.1179, found 370.1179.
Diethyl (2-((2-bromophenyl)carbamoyl)phenyl)phosphonate (3d, CAS NO.: 126391-00-6)
White solid; 67.4 mg, 82% yield; 1H NMR (CDCl3, 500 MHz): δ 8.43 (d, J = 7.9 Hz, 1H), 8.35 (s,
1H), 8.00 (dd, J1 = 14.2 Hz, J2 = 7.6 Hz, 1H), 7.71 (t, J = 6.7 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H),
7.57-7.55 (m, 2H), 7.36 (t, J = 7.4 Hz, 1H), 7.01 (d, J = 8.0 Hz, 1H), 4.17-4.11 (m, 4H), 1.28 (t, J
= 6.8 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 167.1 (d, J = 5.5 Hz), 140.3 (d, J = 9.9 Hz),
136.0, 133.7 (d, J = 8.9 Hz), 132.9 (d, J = 3.3 Hz), 132.7, 130.3 (d, J = 13.5 Hz), 129.1 (d, J =
13.4 Hz), 128.5, 126.0 (d, J = 187.2 Hz), 125.9, 122.8, 114.4, 63.1 (d, J = 6.6 Hz), 16.5 (d, J = 6.6
Hz); 31P NMR (CDCl3, 202 MHz): δ 16.28; IR (film) υmax: 2959, 1665, 1588, 1537, 1483, 1432,
1318, 1223, 1167, 1054, 1012, 965, 753 cm-1; HRMS: [M+Na]+ m/z calcd for C17H19BrNO4PNa+
434.0127, found 434.0127.
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Diethyl (2-((2-iodophenyl)carbamoyl)phenyl)phosphonate (3e, new compound)
White solid; 74.4 mg, 81% yield; 1H NMR (CDCl3, 500 MHz): δ 8.27 (d, J = 7.9 Hz, 1H), 8.18 (s,
1H), 8.01 (dd, J1 = 14.0 Hz, J2 = 7.1 Hz, 1H), 7.81 (dd, J1 = 8.1 Hz, J2 = 1.1 Hz, 1H), 7.75-7.73 (m,
1H), 7.65 (t, J = 7.4 Hz, 1H), 7.59-7.56 (m, 1H), 7.40 (t, J = 7.7 Hz, 1H), 6.91-6.88 (m, 1H),
4.19-4.12 (m, 4H), 1.30 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 167.1 (d, J = 4.4
Hz), 140.3 (d, J = 9.6 Hz), 139.2, 138.6, 133.8 (d, J = 8.8 Hz), 132.9 (d, J = 3.3 Hz), 130.3 (d, J =
14.3 Hz), 129.4, 129.0 (d, J = 13.3 Hz), 128.8, 126.1 (d, J = 187.2 Hz), 123.3, 91.1, 63.2 (d, J =
6.6 Hz), 16.5 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 16.85; IR (film) υmax: 2981, 1682,
1583, 1517, 1431, 1300, 1246, 1142, 1019, 970, 753, 1180, 1142, 1075, 960, 752 cm-1; HRMS:
[M+Na]+ m/z calcd for C17H19INO4PNa+ 481.9989, found 481.9990.
Diethyl (2-((4-fluorophenyl)carbamoyl)phenyl)phosphonate (3f, new compound)
White solid; 56.9 mg, 81% yield; 1H NMR (CDCl3, 500 MHz): δ 9.32 (s, 1H), 7.87-7.83 (m, 2H),
7.70-7.68 (m, 2H), 7.64-7.62 (m, 1H), 7.55-7.52 (m, 1H), 7.03-7.00 (m, 2H), 4.16-4.10 (m, 4H),
1.28 (t, J = 7.3 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.3 (d, J = 5.5 Hz), 159.6 (d, J =
243.2 Hz), 140.1 (d, J = 11.0 Hz), 134.4 (d, J = 2.2 Hz), 133.0 (d, J = 3.3 Hz), 132.6 (d, J = 8.8
Hz), 130.8 (d, J = 13.2 Hz), 130.3 (d, J = 13.3 Hz), 125.2 (d, J = 187.1 Hz), 121.9 (d, J = 7.7 Hz),
115.8 (d, J = 22.1 Hz), 63.5 (d, J = 6.6 Hz), 16.4 (d, J = 6.7 Hz); 31P NMR (CDCl3, 202 MHz): δ
17.80 (d, J = 11.4 Hz); IR (film) υmax: 3258, 3065, 2930, 1675, 1616, 1589, 1549, 1509, 1406,
1323, 1158, 1076, 1026, 972, 835, 791, 751 cm-1; HRMS: [M+Na]+ m/z calcd for
C17H19FNO4PNa+ 374.0928, found 374.0928.
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Diethyl (2-((4-chlorophenyl)carbamoyl)phenyl)phosphonate (3g, new compound)
White solid; 58.7 mg, 80% yield; 1H NMR (CDCl3, 500 MHz): δ 9.44 (s, 1H), 7.87-7.82 (m, 2H),
7.69 (d, J = 8.8 Hz, 2H), 7.63 (t, J = 7.6 Hz, 1H), 7.55-7.52 (m, 1H), 7.29 (d, J = 8.7 Hz, 2H),
4.16-4.11 (m, 4H), 1.28 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.4 (d, J = 4.4
Hz), 140.0 (d, J = 11.0 Hz), 137.1, 133.0 (d, J = 3.3 Hz), 132.6 (d, J = 7.8 Hz), 130.9 (d, J = 13.2
Hz), 130.4 (d, J = 13.4 Hz), 129.5, 129.2, 125.2 (d, J = 187.3 Hz), 121.4, 63.5 (d, J = 5.5 Hz), 16.4
(d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.80; IR (film) υmax: 2968, 1680, 1597, 1539,
1493, 1398, 1318, 1233, 1143, 1093, 1025, 970, 829, 652 cm-1; HRMS: [M+Na]+ m/z calcd for
C17H19ClNO4PNa+ 390.0632, found 390.0629.
Diethyl (2-((4-(trifluoromethyl)phenyl)carbamoyl)phenyl)phosphonate (3h, new compound)
White solid; 62.6 mg, 78% yield; 1H NMR (CDCl3, 500 MHz): δ 9.77 (s, 1H), 7.87-7.80 (m, 4H),
7.64-7.62 (m, 1H), 7.57-7.52 (m, 3H), 4.16-4.10 (m, 4H), 1.29 (t, J = 7.0 Hz, 6H); 13C{1H} NMR
(CDCl3, 125 MHz): δ 166.7 (d, J = 5.4 Hz), 141.6, 139.8 (d, J = 11.0 Hz), 133.0 (d, J = 2.1 Hz),
132.6 (d, J = 8.7 Hz), 130.9 (d, J = 13.1 Hz), 130.5 (d, J = 14.5 Hz), 126.4 (q, J = 3.4 Hz), 126.2
(q, J = 33.2 Hz), 125.3 (d, J = 186.8Hz), 124.4 (q, J = 271.6 Hz), 119.8, 63.5 (d, J = 6.5 Hz), 16.4
(d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.80 (d, J = 9.2 Hz); IR (film) υmax: 2980, 1682,
1606, 1543, 1409, 1323, 1230, 1113, 1066, 1025, 971, 843, 748 cm-1; HRMS: [M+Na]+ m/z calcd
for C18H19F3NO4PNa + 424.0896, found 424.0893.
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Methyl 4-(2-(diethoxyphosphoryl)benzamido)benzoate (3i, new compound)
White solid; 66.5 mg, 85% yield; 1H NMR (CDCl3, 500 MHz): δ 9.64 (s, 1H), 8.00 (d, J = 8.8 Hz,
2H), 7.89-7.80 (m, 4H), 7.64 (t, J = 7.8 Hz, 1H), 7.57-7.54 (m, 1H), 4.16-4.11 (m, 4H), 3.89 (s,
3H), 1.28 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.9, 166.6 (d, J = 5.5 Hz),
142.7, 139.9 (d, J = 10.7 Hz), 133.0 (d, J = 3.2 Hz), 132.6 (d, J = 7.7 Hz), 131.01, 130.96 (d, J =
9.9 Hz), 130.5 (d, J = 14.0 Hz), 125.9, 125.3 (d, J = 187.1 Hz), 119.3, 63.5 (d, J = 6.6 Hz), 52.2,
16.4 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.84; IR (film) υmax: 2974, 1729, 1680,
1602, 1549, 1500, 1442, 1326, 1295, 1251, 1125, 1069, 1022, 970, 759 cm-1; HRMS: [M+Na]+
m/z calcd for C19H22NO6PNa+ 414.1077, found 414.1077.
Diethyl (2-(p-tolylcarbamoyl)phenyl)phosphonate (3j, new compound)
White solid; 62.5 mg, 90% yield; 1H NMR (CDCl3, 500 MHz): δ 9.06 (s, 1H), 7.92-7.87 (m, 2H),
7.65 (t, J = 7.8 Hz, 1H), 7.61 (d, J = 8.3 Hz, 2H), 7.56-7.53 (m, 1H), 7.16 (d, J = 8.1 Hz, 2H),
4.18-4.13 (m, 4H), 2.33 (s, 3H), 1.30 (t, J = 7.0 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ
166.3 (d, J = 4.4 Hz), 140.5 (d, J = 11.0 Hz), 135.9, 134.3, 133.0 (d, J = 3.2 Hz), 132.7 (d, J = 8.9
Hz), 130.9 (d, J = 13.3 Hz), 130.2 (d, J = 13.9 Hz), 129.7, 125.2 (d, J = 187.3 Hz), 120.2, 63.5 (d,
J = 6.6 Hz), 21.2, 16.5 (d, J = 5.5 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.94; IR (film) υmax:
2970, 1670, 1603, 1533, 1515, 1405, 1322, 1236, 1142, 1024, 974, 818 cm-1; HRMS: [M+Na]+
m/z calcd for C18H22NO4PNa+ 370.1179, found 370.1180.
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Diethyl (2-((4-(tert-butyl)phenyl)carbamoyl)phenyl)phosphonate (3k, new compound)
White solid; 66.2 mg, 85% yield; 1H NMR (CDCl3, 500 MHz): δ 9.06 (s, 1H), 7.91-7.85 (m, 2H),
7.65-7.61 (m, 3H), 7.55-7.52 (m, 1H), 7.37-7.35 (m, 2H), 4.17-4.12 (m, 4H), 1.31 (s, 9H), 1.29 (t,
J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.3 (d, J = 5.5 Hz), 147.6, 140.5 (d, J =
11.0 Hz), 135.8, 133.0 (d, J = 3.3 Hz), 132.8 (d, J = 7.7 Hz), 130.8 (d, J = 13.2 Hz), 130.1 (d, J =
13.3 Hz), 126.0, 125.2 (d, J = 186.7 Hz), 120.0, 63.4 (d, J = 6.6 Hz), 34.6, 31.6, 16.4 (d, J = 6.6
Hz); 31P NMR (CDCl3, 202 MHz): δ 17.33; IR (film) υmax: 2960, 1680, 1646, 1602, 1532, 1516,
1404, 1325, 1261, 1021, 834, 754, 648 cm-1; HRMS: [M+H]+ m/z calcd for C21H29NO4P+
390.1829, found 390.1829.
Diethyl (2-((4-methoxyphenyl)carbamoyl)phenyl)phosphonate (3l, new compound)
White solid; 62.5 mg, 86% yield; 1H NMR (CDCl3, 500 MHz): δ 9.05 (s, 1H), 7.91-7.87 (m, 2H),
7.66-7.63 (m, 3H), 7.56-7.53 (m, 1H), 6.91-6.88 (m, 2H), 4.18-4.13 (m, 4H), 3.80 (s, 3H), 1.30 (t,
J = 7.0 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.2 (d, J = 5.5 Hz), 156.7, 140.5 (d, J =
9.9 Hz), 133.0 (d, J = 2.2 Hz), 132.7 (d, J = 7.7 Hz), 131.7, 130.9 (d, J = 13.2 Hz), 130.2 (d, J =
13.3 Hz), 125.2 (d, J = 187.0 Hz), 121.8, 114.4, 63.5 (d, J = 6.6 Hz), 55.7, 16.5 (d, J = 6.6 Hz); 31P
NMR (CDCl3, 202 MHz): δ 17.99; IR (film) υmax: 3649, 1669, 1510, 1244, 1180, 1142, 1022,
971, 832 cm-1; HRMS: [M+H]+ m/z calcd for C18H23NO5P+ 364.1308, found 364.1306.
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Diethyl (2-((4-(methylthio)phenyl)carbamoyl)phenyl)phosphonate (3m, new compound)
White solid; 62.9 mg, 83% yield; 1H NMR (CDCl3, 500 MHz): δ 9.25 (s, 1H), 7.87-7.83 (m, 2H),
7.67-7.65 (m, 2H), 7.62 (t, J = 7.7 Hz, 1H), 7.54-7.51 (m, 1H), 7.25-7.23 (m, 2H), 4.15-4.10 (m,
4H), 2.46 (s, 3H), 1.28 (t, J = 7.0 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.3 (d, J = 4.4
Hz), 140.2 (d, J = 11.1 Hz), 136.1, 133.8, 133.0 (d, J = 3.3 Hz), 132.6 (d, J = 8.8 Hz), 130.8 (d, J
= 13.2 Hz), 130.2 (d, J = 13.7 Hz), 128.0, 125.2 (d, J = 188.2 Hz), 120.7, 63.4 (d, J = 6.6 Hz),
16.8, 16.4 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.79; IR (film) υmax: 2980, 1670,
1594, 1528, 1496, 1397, 1316, 1232, 1142, 1095, 1022, 972, 819 cm-1; HRMS: [M+Na]+ m/z
calcd for C18H22NO4PSNa+ 402.0899, found 402.0896.
Diethyl (2-((2-iodo-4-(trifluoromethyl)phenyl)carbamoyl)phenyl)phosphonate (3n, new
compound)
White solid; 79.1 mg, 75% yield; 1H NMR (CDCl3, 500 MHz): δ 8.46 (d, J = 8.4 Hz, 1H), 8.37 (s,
1H), 8.05 (s, 1H), 8.00 (dd, J1 = 14.0 Hz, J2 = 7.6 Hz, 1H), 7.73 (t, J = 6.1 Hz, 1H), 7.68-7.64 (m,
2H), 7.61-7.58 (m, 1H), 4.18-4.12 (m, 4H), 1.30 (t, J = 7.2 Hz, 6H); 13C{1H} NMR (CDCl3, 125
MHz): δ 167.3 (d, J = 4.4 Hz), 141.8, 139.8 (d, J = 9.9 Hz), 136.2 (q, J = 4.4 Hz), 133.7 (d, J =
8.8 Hz), 133.0 (d, J = 3.2 Hz), 130.6 (d, J = 13.2 Hz), 129.0 (d, J = 12.1 Hz), 128.1 (q, J = 33.3
Hz), 126.6 (q, J = 3.3 Hz), 126.2 (d, J = 187.0Hz), 123.1 (q, J = 271.7 Hz), 122.3, 89.8, 63.2 (d, J
= 5.5 Hz), 16.6 (d, J = 5.5 Hz); 31P NMR (CDCl3, 202 MHz): δ 16.56; IR (film) υmax: 3369, 2984,
1689, 1603, 1577, 1521, 1321, 1303, 1245, 1171, 1126, 1023, 970, 750 568 cm-1; HRMS: [M+H]+
m/z calcd for C18H19F3INO4P+ 528.0034, found 528.0034.
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S17
Diethyl (2-((3-chloro-4-fluorophenyl)carbamoyl)phenyl)phosphonate (3o, new compound)
White solid; 60.1 mg, 78% yield; 1H NMR (CDCl3, 500 MHz): δ 9.69 (s, 1H), 7.93 (dd, J1 = 6.7
Hz, J2 = 2.5 Hz, 1H), 7.82 (t, J = 6.7 Hz, 1H), 7.78 (dd, J1 = 14.2 Hz, J2 = 7.7 Hz, 1H), 7.61 (t, J =
7.5 Hz, 1H), 7.54-7.50 (m, 2H), 7.05 (t, J = 8.9 Hz, 1H), 4.16-4.11 (m, 4H), 1.30 (t, J = 7.1 Hz,
6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.4 (d, J = 4.4 Hz), 154.9 (d, J = 246.4 Hz), 139.8 (d,
J = 11.0 Hz), 135.3 (d, J = 3.3 Hz), 132.9 (d, J = 2.2 Hz), 132.6 (d, J = 7.8 Hz), 130.8 (d, J = 14.3
Hz), 130.4 (d, J = 14.3 Hz), 125.3 (d, J = 187.1 Hz), 122.3, 121.1 (d, J = 18.8 Hz), 119.8 (d, J =
7.7 Hz), 116.6 (d, J = 22.0 Hz), 63.5 (d, J = 6.6 Hz), 16.4 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202
MHz): δ 17.64; IR (film) υmax: 2960, 1672, 1579, 1514, 1428, 1296, 1250, 1024, 985, 772, 692
cm-1; HRMS: [M+Na]+ m/z calcd for C17H18ClFNO4PNa+ 408.0538, found 408.0536.
Diethyl (2-(naphthalen-1-ylcarbamoyl)phenyl)phosphonate (3p, new compound)
White solid; 62.1 mg, 81% yield; 1H NMR (CDCl3, 500 MHz): δ 9.21 (s, 1H), 8.23 (d, J = 7.4 Hz,
1H), 8.04 (d, J = 8.0 Hz, 1H), 7.98 (dd, J1 = 14.2 Hz, J2 = 7.7 Hz, 1H), 7.91 (t, J = 6.8 Hz, 1H),
7.86 (dd, J1 = 6.7 Hz, J2 = 1.9 Hz, 1H), 7.72 (d, J = 8.8 Hz, 1H), 7.67 (t, J = 7.8 Hz, 1H),
7.60-7.57 (m, 1H), 7.54-7.46 (m, 3H), 4.18-4.11 (m, 4H), 1.27 (t, J = 6.9 Hz, 6H); 13C{1H} NMR
(CDCl3, 125 MHz): δ 167.4 (d, J = 4.4 Hz), 140.5 (d, J = 10.0 Hz), 134.3, 130.1 (d, J = 8.7 Hz),
130.06 (d, J = 3.0 Hz), 132.97, 130.5 (d, J = 13.6 Hz), 130.2 (d, J = 13.9 Hz), 128.8, 127.3, 126.4,
126.2, 126.0, 125.9, 125.3 (d, J = 186.7 Hz), 121.4, 120.4, 63.4 (d, J = 6.4 Hz), 16.4 (d, J = 6.4
Hz); 31P NMR (CDCl3, 202 MHz): δ 17.87; IR (film) υmax: 3253, 3058, 2981, 1679, 1607, 1589,
1550, 1506, 1472, 1394, 1360, 1294, 1233, 1143, 1024, 969, 748 cm-1; HRMS: [M+H]+ m/z calcd
for C21H23NO4P+ 384.1359 found 384.1359.
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Diethyl (2-(naphthalen-2-ylcarbamoyl)phenyl)phosphonate (3q, new compound)
White solid; 56.7 mg, 74% yield; 1H NMR (CDCl3, 500 MHz): δ 9.48 (s, 1H), 8.47 (d, J = 1.1 Hz,
1H), 7.94 (t, J = 6.4 Hz, 1H), 7.90 (dd, J1 = 14.3 Hz, J2 = 7.7 Hz, 1H), 7.84 (d, J = 8.1 Hz, 1H),
7.81 (d, J = 8.8 Hz, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.69-7.65 (m, 2H), 7.58-7.55 (m, 1H), 7.46 (t, J
= 7.5 Hz, 1H), 7.40 (t, J = 7.5 Hz, 1H), 4.19-4.13 (m, 4H), 1.29 (t, J = 7.1 Hz, 6H); 13C{1H} NMR
(CDCl3, 125 MHz): δ 166.5 (d, J = 4.4 Hz), 140.3 (d, J = 10.0 Hz), 136.0, 134.1, 130.0 (d, J = 3.3
Hz), 132.6 (d, J = 7.7 Hz), 132.98, 132.97 (d, J = 13.2 Hz), 130.3 (d, J = 13.4 Hz), 128.9, 128.1,
127.7, 126.6, 125.3 (d, J = 187.3 Hz), 125.2, 120.1, 116.9, 63.4 (d, J = 6.6 Hz), 16.4 (d, J = 6.6
Hz); 31P NMR (CDCl3, 202 MHz): δ 18.02; IR (film) υmax: 3239, 2981, 1674, 1538, 1504, 1395,
1346, 1235, 1142, 1023, 967, 797, 796, 773 cm-1; HRMS: [M+H]+ m/z calcd for C21H23NO4P+
384.1359 found 384.1359.
Diethyl (2-(pyridin-2-ylcarbamoyl)phenyl)phosphonate (3r, new compound)
White solid; 54.8 mg, 82% yield; 1H NMR (CDCl3, 500 MHz): δ 9.33 (s, 1H), 8.35 (d, J = 8.4 Hz,
1H), 8.14-8.12 (m, 1H), 7.99 (dd, J1 = 14.2 Hz, J2 = 7.6 Hz, 1H), 7.74-7.71 (m, 2H), 7.62 (t, J =
7.5 Hz, 1H), 7.58-7.55 (m, 1H), 7.02-6.99 (m, 1H), 4.17-4.10 (m, 4H), 1.26 (t, J = 7.2 Hz, 6H);
13C{1H} NMR (CDCl3, 125 MHz): δ 167.4 (d, J = 4.4 Hz), 151.8, 148.2, 140.2 (d, J = 9.9 Hz),
138.5, 133.7 (d, J = 9.4 Hz), 132.9 (d, J = 2.6 Hz), 130.3 (d, J = 14.1 Hz), 129.4 (d, J = 13.1 Hz),
125.8 (d, J = 187.7 Hz), 120.1, 114.3, 63.2 (d, J = 5.5 Hz), 16.3 (d, J = 6.6 Hz); 31P NMR (CDCl3,
202 MHz): δ 16.69; IR (film) υmax: 2960, 1683, 1579, 1533, 1433, 1308, 1243, 1144, 1022, 967,
781 cm-1; HRMS: [M+H]+ m/z calcd for C16H20N2O4P+ 335.1155, found 335.1155.
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Diethyl (E/Z)-(2-(styrylcarbamoyl)phenyl)phosphonate (3s, new compound)
Colorless oil; 53.8 mg, 75% yield; 1H NMR (CDCl3, 500 MHz): δ 8.61 (d, J = 10.7 Hz, 1H),7.97-7.94 (m, 1H), 7.70-7.68 (m, 1H), 7.63-7.61 (m, 1H), 7.56-7.53 (m, 1H), 7.34-7.30 (m, 4H),7.20-7.17 (m, 1H), 7.15-7.11 (m, 1H), 5.87 (d, J = 9.7 Hz, 1H), 4.02-3.97 (m, 4H), 1.81 (t, J = 7.1Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.8 (d, J = 4.9 Hz), 139.3 (d, J = 9.1 Hz), 135.7,135.6 (d, J = 9.4 Hz), 132.9 (d, J = 2.9 Hz), 130.3 (d, J = 13.7 Hz), 129.8 (d, J = 12.8 Hz), 129.2,128.2, 127.2, 125.8 (d, J = 187.2 Hz), 122.1, 111.8, 63.2 (d, J = 6.6 Hz), 16.3 (d, J = 5.6 Hz); 31PNMR (CDCl3, 202 MHz): δ 16.71; IR (film) υmax: 3253, 2977, 2899, 1675, 1598, 1540, 1437,1389, 1321, 1235, 1022, 985, 754 cm-1; HRMS: [M+Na]+ m/z calcd for C19H22NO4PNa+
382.1179, found 382.1179.
Methyl 3-(diethoxyphosphoryl)-4-(phenylcarbamoyl)benzoate (3t, new compound)
White solid; 67.3 mg, 86% yield; 1H NMR (CDCl3, 500 MHz): δ 9.27 (s, 1H), 8.53 (dd, J1 = 14.8Hz, J2 = 1.3 Hz, 1H), 8.28 (d, J = 8.0 Hz, 1H), 7.97 (dd, J1 = 8.0 Hz, J2 = 5.2 Hz, 1H), 7.73 (d, J =7.8 Hz, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.15 (t, J = 7.4 Hz, 1H) 4.22-4.16 (m, 4H), 3.97 (s, 3H), 1.32(t, J = 7.0 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 165.7 (d, J = 1.8 Hz), 165.5 (d, J = 4.6Hz), 144.0 (d, J = 10.9 Hz), 138.2, 133.9 (d, J = 10.0 Hz), 133.8 (d, J = 2.7 Hz), 131.7 (d, J = 13.6Hz), 131.3 (d, J = 12.7 Hz), 129.3, 126.1 (d, J = 189.0 Hz), 125.0, 120.3, 63.8 (d, J = 6.4 Hz), 52.9,16.5 (d, J = 6.4 Hz); 31P NMR (CDCl3, 202 MHz): δ 16.31; IR (film) υmax: 2961, 1732, 1701,1682, 1645, 1545, 1522, 1411, 1331, 1271, 1142, 1022, 970, 762 cm-1; HRMS: [M+Na]+ m/zcalcd for C19H22NO6PNa+ 414.1077, found 414.1077.
Diethyl (4-methyl-2-(phenylcarbamoyl)phenyl)phosphonate (3u, new compound)
White solid; 60.4 mg, 87% yield; 1H NMR (CDCl3, 500 MHz): δ 9.17 (s, 1H), 7.77 (dd, J1 = 14.1
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S20
Hz, J2 = 7.8 Hz, 1H), 7.71 (d, J = 8.0 Hz, 2H), 7.69 (d, J = 4.8 Hz, 1H), 7.34 (t, J = 7.0 Hz, 3H),
7.11 (t, J = 7.3 Hz, 1H), 4.14-4.09 (m, 4H), 2.42 (s, 3H), 1.27 (t, J = 7.0 Hz, 6H); 13C{1H} NMR
(CDCl3, 125 MHz): δ 166.6 (d, J = 5.5 Hz), 143.8 (d, J = 2.2 Hz), 140.2 (d, J = 11.0 Hz), 138.5,
132.9 (d, J = 8.8 Hz), 131.5 (d, J = 13.5 Hz), 130.8 (d, J = 14.3 Hz), 129.2, 124.6, 121.9 (d, J =
189.4 Hz), 120.1, 63.3 (d, J = 6.7 Hz), 21.6, 16.4 (d, J = 6.7 Hz); 31P NMR (CDCl3, 202 MHz): δ
18.60; IR (film) υmax: 3255, 2981, 1679, 1600, 1543, 1500, 1442, 1393, 1324, 1232, 1025, 970,
756, 694 cm-1; HRMS: [M+Na]+ m/z calcd for C18H22NO4PNa+ 370.1179, found 370.1178.
Diethyl (4-methoxy-2-(phenylcarbamoyl)phenyl)phosphonate (3v, new compound)
White solid; 61.7 mg, 85% yield; 1H NMR (CDCl3, 500 MHz): δ 9.28 (s, 1H), 7.81 (dd, J1 = 13.5
Hz, J2 = 8.6 Hz, 1H), 7.72 (d, J = 7.7 Hz, 2H), 7.40 (dd, J1 = 4.5 Hz, J2 = 2.7 Hz, 1H), 7.34 (t, J =
7.6 Hz, 2H), 7.12 (t, J = 7.4 Hz, 1H), 7.02 (dt, J1 = 8.5 Hz, J2 = 2.5 Hz, 1H), 4.14-4.08 (m, 4H),
3.87 (s, 3H), 1.27 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.1 (d, J = 4.4 Hz),
163.1 (d, J = 3.3 Hz), 142.4 (d, J = 12.1 Hz), 138.4, 135.0 (d, J = 8.8 Hz), 129.2, 124.6, 120.2,
116.4 (d, J = 194.0 Hz), 116.1 (d, J = 15.4 Hz), 116.0 (d, J = 14.3 Hz), 63.2 (d, J = 6.6 Hz), 55.8,
16.4 (d, J = 5.5 Hz); 31P NMR (CDCl3, 202 MHz): δ 18.89; IR (film) υmax: 2972, 1663, 1562,
1501, 1478, 1244, 1170, 1132, 1076, 1016, 965, 825, 782 cm-1; HRMS: [M+Na]+ m/z calcd for
C18H22NO5PNa+ 386.1128, found 386.1124.
Diethyl (4-chloro-2-(phenylcarbamoyl)phenyl)phosphonate (3w, new compound)
White solid; 59.5 mg, 81% yield; 1H NMR (CDCl3, 500 MHz): δ 9.22 (s, 1H), 7.88 (dd, J1 = 4.3
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Hz, J2 = 2.0 Hz, 1H), 7.82 (dd, J1 = 13.8 Hz, J2 = 8.3 Hz, 1H), 7.70 (d, J = 7.9 Hz, 2H), 7.51 (dt, J1
= 8.2 Hz, J2 = 2.4 Hz, 1H), 7.35 (t, J = 8.1 Hz, 2H), 7.14 (t, J = 7.4 Hz, 1H), 4.14-4.13 (m, 4H),
1.29 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 164.9 (d, J = 4.4 Hz), 161.9 (d, J =
11.0 Hz), 139.7 (d, J = 3.3 Hz), 138.2, 134.3 (d, J = 8.8 Hz), 131.1 (d, J = 13.2 Hz), 130.3 (d, J =
15.4 Hz), 129.3, 124.9, 123.7 (d, J = 190.4 Hz), 120.2, 63.7 (d, J = 6.6 Hz), 16.4 (d, J = 5.5 Hz);
31P NMR (CDCl3, 202 MHz): δ 16.90; IR (film) υmax: 2965, 1672, 1589, 1532, 1481, 1395, 1318,
1225, 1089, 1019, 962, 826, 595 cm-1; HRMS: [M+Na]+ m/z calcd for C17H19ClNO4PNa+
390.0632, found 390.0631.
Diethyl (4-bromo-2-(phenylcarbamoyl)phenyl)phosphonate (3x, new compound)
White solid; 70.7 mg, 86% yield; 1H NMR (CDCl3, 500 MHz): δ 9.19 (s, 1H), 8.03 (dd, J1 = 4.5
Hz, J2 = 1.8 Hz, 1H), 7.74 (dd, J1 = 13.7 Hz, J2 = 8.3 Hz, 1H), 7.71-7.67 (m, 3H), 7.35 (t, J = 7.6
Hz, 2H), 7.14 (t, J = 7.5 Hz, 1H), 4.17-4.12 (m, 4H), 1.29 (t, J = 7.0 Hz, 6H); 13C{1H} NMR
(CDCl3, 125 MHz): δ 164.8 (d, J = 4.4 Hz), 141.8 (d, J = 12.1 Hz), 138.2, 134.2 (d, J = 9.9 Hz),
133.9 (d, J = 14.3 Hz), 133.3 (d, J = 14.4 Hz), 129.3, 128.1 (d, J = 4.4 Hz), 124.9, 124.2 (d, J =
189.8 Hz), 120.2, 63.7 (d, J = 6.6 Hz), 16.4 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.03;
IR (film) υmax: 2962, 1680, 1599, 1544, 1500, 1322, 1235, 1067, 1021, 973, 770, 693 cm-1;
HRMS: [M+Na]+ m/z calcd for C17H19BrNO4PNa+ 434.0127, found 434.1027.
Diethyl (2-(phenylcarbamoyl)thiophen-3-yl)phosphonate (3y, new compound)
White solid; 59.0 mg, 87% yield; 1H NMR (CDCl3, 500 MHz): δ 12.12 (s, 1H), 7.80 (dd, J1 = 8.3
Hz, J2 = 0.7 Hz, 2H), 7.55 (dd, J1 = 5.5 Hz, J2 = 2.2 Hz, 1H), 7.34 (t, J = 7.6 Hz, 2H), 7.30 (t, J =
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S22
4.8 Hz, 1H), 7.11 (t, J = 7.3 Hz, 1H), 4.24-4.11 (m, 4H), 1.34 (t, J = 7.1 Hz, 6H); 13C{1H} NMR
(CDCl3, 125 MHz): δ 158.7 (d, J = 3.3 Hz), 151.5 (d, J = 20.9 Hz), 138.8, 132.8 (d, J = 13.2 Hz),
130.4 (d, J = 18.7 Hz), 129.1, 125.3 (d, J = 187.7 Hz), 124.5, 120.3, 63.5 (d, J = 5.5 Hz), 16.4 (d, J
= 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 14.03; IR (film) υmax: 2983, 1772, 1604, 1553, 1492,
1462, 1390, 1285, 1183, 1114, 1019, 997, 754 cm-1; HRMS: [M+Na]+ m/z calcd for
C15H18NO4PSNa+ 362.0586, found 362.0586.
Dimethyl (2-(phenylcarbamoyl)phenyl)phosphonate (4a, CAS NO.: 460836-90-0)
White solid; 54.9 mg, 90% yield; 1H NMR (CDCl3, 500 MHz): δ 9.02 (s, 1H), 7.87-7.83 (m, 2H),
7.71 (d, J = 8.1 Hz, 2H), 7.64 (t, J = 7.7 Hz, 1H), 7.56-7.53 (m, 1H), 7.34 (t, J = 7.4 Hz, 2H), 7.13
(t, J = 7.3 Hz, 1H), 3.77 (t, J = 11.0 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.5 (d, J =
4.4 Hz), 140.6 (d, J = 10.3 Hz), 138.4, 133.2 (d, J = 2.4 Hz), 133.0 (d, J = 7.9 Hz), 130.5 (d, J =
13.3 Hz), 130.3 (d, J = 14.1 Hz), 129.3, 124.8, 134.2 (d, J = 188.0 Hz), 120.3, 53.8 (d, J = 6.1 Hz);
31P NMR (CDCl3, 202 MHz): δ 20.33; IR (film) υmax: 3251, 2960, 1670, 1601, 1544, 1492, 1442,
1324, 1241, 1031, 836, 788, 758 cm-1; HRMS: [M+Na]+ m/z calcd for C15H16NO4PNa+ 328.0709,
found 328.0709.
Diisopropyl (2-(phenylcarbamoyl)phenyl)phosphonate (4b, CAS NO.: 60815-47-6)
White solid; 62.8 mg, 87% yield; 1H NMR (CDCl3, 500 MHz): δ 9.41 (s, 1H), 7.92-7.84 (m, 2H),
7.71 (d, J = 8.2 Hz, 2H), 7.58 (t, J = 7.5 Hz, 1H), 7.50 (t, J = 8.2 Hz, 1H), 7.31 (t, J = 7.8 Hz, 2H),
7.08 (t, J = 7.2 Hz, 1H), 4.77-4.72 (m, 2H), 1.27-1.24 (m, 12H); 13C{1H} NMR (CDCl3, 125
MHz): δ 166.3 (d, J = 5.5 Hz), 140.1 (d, J = 11.0 Hz), 138.5, 132.63 (d, J = 3.3 Hz), 132.57 (d, J
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S23
= 9.1 Hz), 130.9 (d, J = 13.2 Hz), 130.0 (d, J = 14.1 Hz), 129.0, 126.4 (d, J = 188.1 Hz), 124.4,
120.1, 72.4 (d, J = 6.5 Hz), 24.1 (d, J = 4.3 Hz), 23.9 (d, J = 4.4 Hz); 31P NMR (CDCl3, 202
MHz): δ 15.81; IR (film) υmax: 3261, 3063, 2979, 2934, 1680, 1601, 1544, 1499, 1442, 1386,
1375, 1322, 1230, 1142, 1105, 1072, 995, 756 570 cm-1; HRMS: [M+Na]+ m/z calcd for
C19H24NO4PNa+ 384.1335, found 384.1334.
Diisopropyl (2-(phenylcarbamoyl)thiophen-3-yl)phosphonate (4c, new compound)
White solid; 63.1 mg, 86% yield; 1H NMR (CDCl3, 500 MHz): δ 12.25 (s, 1H), 7.81 (d, J = 7.7
Hz, 2H), 7.53 (dd, J1 = 5.1 Hz, J2 = 2.3 Hz, 1H), 7.35-7.30 (m, 3H), 7.11 (t, J = 7.4 Hz, 1H),
4.78-4.72 (m, 2H), 1.39 (d, J = 6.2 Hz, 6H), 1.26 (d, J = 6.2 Hz, 6H); 13C{1H} NMR (CDCl3, 125
MHz): δ 158.9 (d, J = 3.3 Hz), 150.9 (d, J = 20.7 Hz), 138.9, 133.1 (d, J = 12.1 Hz), 130.2 (d, J =
19.0 Hz), 129.1, 127.0 (d, J = 189.1 Hz), 124.4, 120.4, 72.7 (d, J = 5.6 Hz), 24.2 (d, J = 4.2 Hz),
23.9 (d, J = 4.4 Hz); 31P NMR (CDCl3, 202 MHz): δ 11.53 IR (film) υmax: 2962, 1660, 1627,
1565, 1489, 1447, 1398, 1324, 1270, 1225, 1167, 1020, 976, 844, 758 cm-1; HRMS: [M+Na]+ m/z
calcd for C17H22NO4PSNa+ 390.0899, found 390.0904.
Dibutyl (2-(phenylcarbamoyl)phenyl)phosphonate (4d, new compound)
White solid; 63.1 mg, 81% yield; 1H NMR (CDCl3, 500 MHz): δ 9.28 (s, 1H), 7.86-7.83 (m, 2H),
7.72 (d, J = 8.3 Hz, 2H), 7.60 (t, J = 7.7 Hz, 1H), 7.51 (t, J = 7.7 Hz, 1H), 7.33-7.30 (m, 2H), 7.09
(t, J = 6.6 Hz, 1H), 4.07-4.03 (m, 4H), 1.61-1.56 (m, 4H), 1.32-1.26 (m, 4H), 0.83-0.80 (m, 6H);
13C{1H} NMR (CDCl3, 125 MHz): δ 166.3 (d, J = 5.3 Hz), 140.2 (d, J = 10.0 Hz), 138.5, 132.9
(d, J = 2.2 Hz), 132.5 (d, J = 7.7 Hz), 130.8 (d, J = 13.6 Hz), 130.1 (d, J = 13.5 Hz), 129.0, 125.2
-
S24
(d, J = 188.0 Hz), 124.5, 120.0, 67.1 (d, J = 6.6 Hz), 32.5 (d, J = 6.6 Hz), 18.8, 13.6; 31P NMR
(CDCl3, 202 MHz): δ 20.33; IR (film) υmax: 3254, 3133, 3061, 2961, 2873, 1679, 1602, 1545,
1499, 1465, 1442, 1323, 1228, 1074, 1024, 757, 693, 571 cm-1; HRMS: [M+Na]+ m/z calcd for
C21H28NO4PNa+ 412.1648, found 412.1649.
Ethyl phenyl(2-(phenylcarbamoyl)phenyl)phosphinate (4f, new compound)
White solid; 65.0 mg, 89% yield; 1H NMR (CDCl3, 500 MHz): δ 9.70 (s, 1H), 7.91-7.89 (m, 1H),
7.72-7.68 (m, 4H), 7.63-7.59 (m, 2H), 7.56-7.53 (m, 1H), 7.49-7.46 (m, 1H), 7.42-7.39 (m, 2H),
7.32 (t, J = 7.9 Hz, 2H), 7.11 (t, J = 7.3 Hz, 1H), 4.14-4.07 (m, 1H), 3.97-3.90 (m, 1H), 1.21 (t, J =
7.2 Hz, 3H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.2 (d, J = 4.4 Hz), 140.6 (d, J = 10.0 Hz),
138.5, 133.2 (d, J = 2.7 Hz), 132.8 (d, J = 2.2 Hz), 132.5 (d, J = 10.8 Hz), 132.1 (d, J = 10.5 Hz),
131.2 (d, J = 11.2 Hz), 130.1 (d, J = 13.0 Hz), 129.2 (d, J = 134.7 Hz), 129.1, 128.9 (d, J = 13.3
Hz), 128.8 (d, J = 136.8 Hz), 124.5, 120.0, 62.1 (d, J = 5.6 Hz), 16.4 (d, J = 6.6 Hz); 31P NMR
(CDCl3, 202 MHz): δ 35.66; IR (film) υmax: 3121, 2490, 1680, 1649, 1601, 1549, 1440, 1324,
1260, 1142, 1032, 799, 758, 693 cm-1; HRMS: [M+H]+ m/z calcd for C21H21NO3P+ 366.1254,
found 366.1256.
3-(Diphenylphosphoryl)-N-phenylthiophene-2-carboxamide (4g, new compound)
White solid; 69.3 mg, 86% yield; 1H NMR (CDCl3, 500 MHz): δ 12.49 (s, 1H), 7.77 (d, J = 7.7
Hz, 2H), 8.67-8.64 (m, 4H), 7.60-7.58 (m, 2H), 7.51-7.48 (m, 5H), 7.30 (t, J = 7.7 Hz, 2H), 7.08 (t,
-
S25
J = 7.3 Hz, 1H), 6.70 (t, J = 5.2 Hz, 1H); 13C{1H} NMR (CDCl3, 125 MHz): δ 159.1 (d, J = 2.2
Hz), 152.6 (d, J = 11.0 Hz), 138.9, 133.5 (d, J = 16.5 Hz), 133.1 (d, J = 2.9 Hz), 132.0 (d, J = 10.8
Hz), 131.4 (d, J = 108.9 Hz), 129.9 (d, J = 16.5 Hz), 129.6 (d, J = 101.4 Hz), 129.2 (d, J = 13.1
Hz), 129.0, 124.4, 120.4; 31P NMR (CDCl3, 202 MHz): δ 29.27; IR (film) υmax: 2960, 1716,
1688, 1601, 1533, 1408, 1279, 1260, 1178, 1143, 1112, 1024, 971, 770 cm-1; HRMS: [M+H]+ m/z
calcd for C23H19NO2PS+ 404.0869, found 404.0869.
2-(Diphenylphosphoryl)-N-phenylbenzamide (4h, new compound)
White solid; 66.7 mg, 84% yield; 1H NMR (CDCl3, 500 MHz): δ 10.54 (s, 1H), 8.08-8.06 (m,
1H), 7.68-7.63 (m, 5H), 7.51-7.49 (m, 2H), 7.44-7.39 (m, 7H), 7.21-7.19 (m, 2H), 7.14-7.10 (m,
1H), 7.04-7.01 (m, 1H); 13C{1H} NMR (CDCl3, 125 MHz): δ 165.4 (d, J = 4.4 Hz), 141.3 (d, J =
8.3 Hz), 137.9, 133.2 (d, J = 11.9 Hz), 132.8 (d, J = 3.3 Hz), 132.4 (d, J = 3.3 Hz), 132.3 (d, J =
8.9 Hz), 131.6 (d, J = 10.2 Hz), 130.5 (d, J = 94.8 Hz), 130.1, 129.6 (d, J = 98.0 Hz), 128.7 (d, J =
12.5 Hz), 128.5, 124.1, 120.1; 31P NMR (CDCl3, 202 MHz): δ 34.45; IR (film) υmax: 3062, 1670,
1601, 1549, 1499, 1438, 1325, 1180, 1120, 1075, 756, 727, 692, 542 cm-1; HRMS: [M+H]+ m/z
calcd for C25H21NO2P+ 398.1304, found 398.1302.
N-(4-Chlorophenyl)-2-(diphenylphosphoryl)benzamide (4i, new compound)
White solid; 74.1 mg, 86% yield; 1H NMR (CDCl3, 500 MHz): δ 10.73 (s, 1H), 8.08 (dd, J1 = 7.9
Hz, J2 = 4.1 Hz, 1H), 7.70-7.67 (m, 1H), 7.66-7.62 (m, 4H), 7.54-7.51 (m, 2H), 7.46-7.40 (m, 7H),
7.19-7.16 (m, 2H), 7.12 (dd, J1 = 14.0 Hz, J2 = 7.3 Hz, 1H); 13C{1H} NMR (CDCl3, 125 MHz): δ
165.6 (d, J = 3.8 Hz), 141.1 (d, J = 8.8 Hz), 136.8, 133.5 (d, J = 11.8 Hz), 133.0 (d, J = 2.2 Hz),
-
S26
132.7 (d, J = 3.2 Hz), 132.5 (d, J = 9.4 Hz), 131.7 (d, J = 9.9 Hz), 130.5 (d, J = 12.1 Hz), 130.4 (d,
J = 106.4 Hz), 129.14, 129.08 (d, J = 105.7 Hz), 128.9 (d, J = 12.3 Hz), 128.7, 121.5; 31P NMR
(CDCl3, 202 MHz): δ 35.84; IR (film) υmax: 3061, 1702, 1692, 1653, 1606, 1543, 1458, 1337,
1258, 1152, 1064, 1030, 976, 755 cm-1; HRMS: [M+H]+ m/z calcd for C25H20ClNO2P+ 432.0915,
found 432.0912.
2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-N-(m-tolyl)benzamide (6a, new compound)
White solid; 47.2 mg, 70% yield; 1H NMR (CDCl3, 500 MHz): δ 7.09 (s, 1H), 7.86 (d, J = 7.3 Hz,
2H), 7.54-7.51 (m, 1H), 7.46 (t, J = 8.0 Hz, 2H), 7.42 (d, J = 8.1 Hz, 1H), 7.24 (t, J = 7.8 Hz, 1H),
6.96 (d, J = 7.7 Hz, 1H), 2.35 (s, 3H), 1.25 (s, 12H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.0,
139.2, 135.3, 138.1, 132.0, 129.1, 129.0, 127.2, 125.6, 121.1, 117.5, 83.7, 25.2, 21.7; IR (film)
υmax: 2978, 1748, 1688, 1649, 1612, 1544, 1489 1281, 1124, 1030, 848, 780, 692 cm-1; HRMS:
[M+Na]+ m/z calcd for C20H24BNO3Na+ 360.1741, found 360.1740.
N-Phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene-2-carboxamide (6b, new
compound)
White solid; 42.8 mg, 65% yield; 1H NMR (CDCl3, 500 MHz): δ 10.75 (s, 1H), 7.73-7.71 (m,
2H), 7.51 (s, 2H), 7.38-7.35 (m, 2H), 7.14-7.11 (m, 1H), 1.45 (s, 12H); 13C{1H} NMR (CDCl3,
125 MHz): δ 160.5, 151.9, 139.1, 136.4, 130.1, 129.3, 124.2, 120.0, 85.6, 25.1; IR (film) υmax:
2976, 1754, 1744, 1678, 1642, 1609, 1558, 1482, 1280, 1142, 1021, 853, 778 cm-1; HRMS:
[M+H]+ m/z calcd for C17H21BNO3S+ 330.1330, found 330.1328.
-
S27
8. 1H, 13C and 31P spectrum for all the products.
10 9 8 7 6 5 4 3 2 1 0 ppm
1.271
1.282
1.294
4.119
4.132
4.144
4.155
4.157
4.167
4.169
7.113
7.125
7.137
7.331
7.344
7.357
7.526
7.528
7.532
7.533
7.539
7.540
7.544
7.546
7.551
7.553
7.557
7.558
7.627
7.640
7.652
7.715
7.727
7.856
7.867
7.879
7.891
7.892
7.904
7.905
9.152
6.00
4.02
0.99
2.01
1.02
1.00
2.00
2.02
1.00
NH
OPh
PO
EtOEtO
1H NMR spectrum of compound 3a
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.43
16.47
63.46
63.50
120.18
124.61
124.69
125.85
129.23
130.21
130.30
130.75
130.84
132.73
132.79
133.04
133.06
138.49
140.36
140.43
166.46
166.49
NH
OPh
PO
EtOEtO
13C NMR spectrum of compound 3a
-
S28
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.78
NH
OPh
PO
EtOEtO
31P NMR spectrum of compound 3a
10 9 8 7 6 5 4 3 2 1 0 ppm
1.281
1.293
1.305
2.353
4.126
4.138
4.150
4.162
4.175
6.938
6.950
7.213
7.226
7.239
7.511
7.525
7.538
7.543
7.555
7.626
7.639
7.651
7.854
7.867
7.876
7.880
7.892
7.904
9.089
6.00
2.98
4.00
1.00
1.00
3.01
1.01
1.99
1.00
NH
OPO
EtOEtO
Me
1H NMR spectrum of compound 3b
-
S29
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.40
16.45
21.75
63.42
63.46
117.25
120.71
124.54
125.49
125.78
129.01
130.13
130.22
130.74
130.83
132.67
132.73
133.00
133.01
138.37
139.06
140.42
140.49
166.36
166.40
NH
OPO
EtOEtO
Me
13C NMR spectrum of compound 3b
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.87
NH
OPO
EtOEtO
Me
31P NMR spectrum of compound 3b
-
S30
10 9 8 7 6 5 4 3 2 1 0 ppm
1.293
1.305
1.317
2.313
4.125
4.137
4.149
4.162
4.174
7.080
7.092
7.104
7.190
7.202
7.225
7.238
7.251
7.538
7.543
7.551
7.556
7.563
7.568
7.630
7.643
7.656
7.813
7.824
7.835
7.905
7.918
7.929
7.941
8.015
8.028
8.515
6.00
3.00
4.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
0.99
1.00
NH
OPO
EtOEtO
Me
1H NMR spectrum of compound 3c
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.41
16.46
18.04
63.30
63.34
123.05
124.73
125.54
125.97
126.81
129.97
130.06
130.16
130.25
130.34
130.75
132.93
132.98
136.10
140.53
140.60
166.80
166.83
NH
OPO
EtOEtO
Me
13C NMR spectrum of compound 3c
-
S31
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.57
NH
OPO
EtOEtO
Me
31P NMR spectrum of compound 3c
10 9 8 7 6 5 4 3 2 1 0 ppm
1.267
1.279
1.291
4.107
4.112
4.118
4.124
4.130
4.137
4.142
4.149
4.154
4.160
4.167
4.171
7.001
7.014
7.027
7.344
7.357
7.369
7.545
7.559
7.568
7.573
7.580
7.585
7.629
7.642
7.654
7.699
7.708
7.720
7.981
7.994
8.005
8.018
8.355
8.419
8.433
6.00
4.01
1.00
1.01
2.00
1.00
0.99
1.00
0.96
1.00
NH
OPO
EtOEtO
Br
1H NMR spectrum of compound 3d
-
S32
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.45
16.49
63.11
63.15
114.36
122.79
125.38
125.92
126.62
128.53
129.05
129.14
130.22
130.31
132.65
132.92
132.94
133.69
133.75
136.00
140.24
140.31
167.08
NH
OPO
EtOEtO
Br
13C NMR spectrum of compound 3d
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.28
NH
OPO
EtOEtO
Br
31P NMR spectrum of compound 3d
-
S33
10 9 8 7 6 5 4 3 2 1 0 ppm
1.285
1.297
1.309
4.123
4.128
4.136
4.140
4.148
4.152
4.154
4.160
4.166
4.172
4.177
4.184
4.189
6.878
6.880
6.891
6.892
6.903
6.905
7.382
7.395
7.408
7.563
7.569
7.576
7.580
7.588
7.593
7.642
7.654
7.667
7.732
7.741
7.752
7.801
7.803
7.814
7.816
7.988
8.001
8.011
8.024
8.179
6.02
4.01
1.00
1.01
1.00
1.01
1.00
1.00
1.00
1.00
1.00
NH
OPO
EtOEtO
I
1H NMR spectrum of compound 3e
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.52
16.57
63.14
63.18
91.14
123.27
125.47
126.70
126.82
129.00
129.08
129.41
130.23
130.32
132.95
133.74
133.80
138.62
139.21
140.27
140.34
167.07
NH
OPO
EtOEtO
I
13C NMR spectrum of compound 3e
-
S34
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.85
NH
OPO
EtOEtO
I
31P NMR spectrum of compound 3e
10 9 8 7 6 5 4 3 2 1 0 ppm
1.270
1.282
1.294
4.103
4.108
4.110
4.115
4.120
4.122
4.133
4.135
4.144
4.147
4.156
4.159
4.164
6.999
7.004
7.008
7.019
7.029
7.033
7.518
7.520
7.523
7.525
7.530
7.532
7.536
7.538
7.543
7.545
7.548
7.550
7.617
7.620
7.630
7.632
7.640
7.643
7.645
7.680
7.683
7.688
7.692
7.695
7.699
7.703
7.830
5.99
4.00
2.00
1.01
1.00
2.00
2.00
0.99
NH
OPO
EtOEtO F
1H NMR spectrum of compound 3f
-
S35
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.39
16.44
63.44
63.49
115.72
115.87
121.86
121.91
124.56
125.80
130.24
130.33
130.76
130.84
132.61
132.67
133.00
133.01
134.56
134.57
140.10
140.17
158.84
160.45
166.33
166.36
NH
OPO
EtOEtO F
13C NMR spectrum of compound 3f
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.78
17.82
NH
OPO
EtOEtO F
31P NMR spectrum of compound 3f
-
S36
10 9 8 7 6 5 4 3 2 1 0 ppm
1.271
1.283
1.295
4.107
4.108
4.120
4.132
4.143
4.145
4.155
4.157
7.279
7.293
7.523
7.528
7.535
7.539
7.548
7.552
7.620
7.632
7.645
7.680
7.695
7.823
7.835
7.847
7.859
7.870
9.436
6.00
4.00
2.00
1.02
1.01
2.01
1.99
0.99
NH
OPO
EtOEtO Cl
1H NMR spectrum of compound 3g
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.40
16.44
63.48
63.52
121.37
124.58
125.82
129.17
129.50
130.32
130.41
130.82
130.91
132.57
132.62
133.00
133.02
137.14
139.97
140.05
166.37
166.40
NH
OPO
EtOEtO Cl
13C NMR spectrum of compound 3g
-
S37
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.80
NH
OPO
EtOEtO Cl
31P NMR spectrum of compound 3g
10 9 8 7 6 5 4 3 2 1 0 ppm
1.277
1.289
1.301
4.104
4.111
4.116
4.123
4.127
4.136
4.145
4.148
4.153
4.160
4.165
7.523
7.528
7.535
7.541
7.549
7.560
7.569
7.618
7.631
7.643
7.799
7.812
7.822
7.836
7.846
7.859
7.869
9.765
6.00
4.00
3.00
1.00
3.99
0.99
NH
OPO
EtOEtO CF3
1H NMR spectrum of compound 3h
-
S38
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.39
16.43
63.50
63.54
119.82
121.66
123.46
124.71
125.26
125.87
125.95
126.08
126.30
126.31
126.34
126.37
126.39
126.52
127.07
130.44
130.53
130.81
130.89
132.61
132.66
132.97
132.99
139.80
139.88
141.63
166.68
166.72
NH
OPO
EtOEtO CF3
13C NMR spectrum of compound 3h
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.78
17.82
NH
OPO
EtOEtO CF3
31P NMR spectrum of compound 3h
-
S39
10 9 8 7 6 5 4 3 2 1 0 ppm
1.264
1.275
1.287
3.885
4.110
4.112
4.122
4.124
4.135
4.146
4.149
4.158
4.161
7.537
7.542
7.550
7.555
7.562
7.566
7.632
7.645
7.658
7.805
7.819
7.830
7.843
7.854
7.867
7.878
7.889
8.001
8.015
9.637
5.99
3.00
4.00
1.00
1.00
3.99
2.00
1.00
NH
OPO
EtOEtO CO2Me
1H NMR spectrum of compound 3i
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.40
16.44
52.20
63.52
63.56
119.31
124.69
125.91
125.93
130.47
130.56
130.93
131.01
132.57
132.63
133.03
133.05
139.82
139.89
142.69
166.60
166.64
166.89
NH
OPO
EtOEtO CO2Me
13C NMR spectrum of compound 3i
-
S40
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.84
NH
OPO
EtOEtO CO2Me
31P NMR spectrum of compound 3i
10 9 8 7 6 5 4 3 2 1 0 ppm
1.284
1.296
1.308
2.330
4.131
4.143
4.154
4.166
4.180
7.149
7.162
7.532
7.537
7.544
7.549
7.550
7.557
7.561
7.601
7.615
7.636
7.649
7.662
7.874
7.881
7.894
7.904
7.916
9.056
6.00
2.99
4.00
2.00
1.00
1.99
0.99
2.00
1.00
NH
OPO
EtOEtO Me
1H NMR spectrum of compound 3j
-
S41
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.44
16.48
21.16
63.43
63.48
120.17
124.56
125.80
129.73
130.13
130.22
130.81
130.90
132.72
132.78
133.02
133.04
134.28
135.94
140.45
140.52
166.26
166.29
NH
OPO
EtOEtO Me
13C NMR spectrum of compound 3j
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.94
NH
OPO
EtOEtO Me
31P NMR spectrum of compound 3j
-
S42
10 9 8 7 6 5 4 3 2 1 0 ppm
1.282
1.293
1.308
4.124
4.136
4.148
4.160
4.173
7.347
7.352
7.355
7.363
7.366
7.370
7.519
7.524
7.532
7.537
7.544
7.550
7.612
7.618
7.622
7.632
7.642
7.645
7.648
7.851
7.858
7.862
7.864
7.872
7.875
7.877
7.889
7.900
7.912
9.059
14.95
4.00
2.00
1.00
3.00
2.00
1.00
NH
OPO
EtOEtO tBu
1H NMR spectrum of compound 3k
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.41
16.46
31.57
34.59
63.39
63.43
119.97
124.54
125.77
125.99
130.07
130.16
130.71
130.80
132.77
132.83
132.98
133.00
135.78
140.45
140.52
147.57
166.30
166.33
NH
OPO
EtOEtO tBu
13C NMR spectrum of compound 3k
-
S43
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.33
NH
OPO
EtOEtO tBu
31P NMR spectrum of compound 3k
10 9 8 7 6 5 4 3 2 1 0 ppm
1.288
1.300
1.311
3.804
4.132
4.144
4.155
4.157
4.168
4.169
4.179
4.181
6.880
6.885
6.889
6.897
6.901
6.906
7.528
7.530
7.533
7.536
7.540
7.543
7.546
7.548
7.553
7.555
7.559
7.561
7.633
7.638
7.641
7.646
7.649
7.653
7.659
7.661
7.664
7.872
7.875
7.877
7.884
7.886
7.890
5.99
3.00
4.00
2.00
1.00
2.99
1.99
1.00
NH
OPO
EtOEtO OMe
1H NMR spectrum of compound 3l
-
S44
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.45
16.50
55.70
63.44
63.48
114.38
121.83
124.56
125.80
130.12
130.21
130.81
130.90
131.73
132.71
132.77
133.03
133.04
140.44
140.50
156.71
166.15
166.19
NH
OPO
EtOEtO OMe
13C NMR spectrum of compound 3l
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.99
NH
OPO
EtOEtO OMe
31P NMR spectrum of compound 3l
-
S45
10 9 8 7 6 5 4 3 2 1 0 ppm
1.264
1.276
1.287
2.455
4.103
4.114
4.126
4.139
4.141
4.151
4.153
7.227
7.232
7.236
7.243
7.247
7.251
7.510
7.516
7.523
7.528
7.535
7.540
7.609
7.621
7.634
7.647
7.651
7.655
7.662
7.666
7.670
7.832
7.834
7.835
7.843
7.846
7.848
7.855
7.857
7.859
7.870
7.872
6.01
2.99
4.00
1.99
1.00
1.00
1.99
2.00
1.00
NH
OPO
EtOEtO SMe
1H NMR spectrum of compound 3m
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.39
16.43
16.77
63.41
63.45
120.69
124.54
125.78
128.05
130.17
130.26
130.71
130.80
132.61
132.67
132.95
132.97
133.80
136.13
140.16
140.23
166.27
166.30
NH
OPO
EtOEtO SMe
13C NMR spectrum of compound 3m
-
S46
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.79
NH
OPO
EtOEtO SMe
31P NMR spectrum of compound 3m
10 9 8 7 6 5 4 3 2 1 0 ppm
1.284
1.296
1.308
4.117
4.122
4.128
4.134
4.139
4.147
4.152
4.159
4.164
4.171
4.176
4.181
7.583
7.589
7.596
7.600
7.601
7.607
7.609
7.612
7.614
7.643
7.654
7.664
7.677
7.717
7.726
7.738
7.972
7.985
7.995
8.008
8.048
8.370
8.448
8.462
6.01
4.00
1.01
2.00
1.00
1.00
0.99
1.00
1.00
NH
OPO
EtOEtO
I
CF3
1H NMR spectrum of compound 3n
-
S47
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.53
16.57
63.20
63.24
89.76
120.36
122.16
122.30
123.97
125.61
125.77
126.57
126.59
126.85
127.81
128.03
128.25
128.48
128.99
129.07
130.54
130.63
132.97
132.99
133.64
133.70
136.17
136.19
136.22
139.76
139.82
141.80
167.30
167.33
NH
OPO
EtOEtO
I
CF3
13C NMR spectrum of compound 3n
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.56
NH
OPO
EtOEtO
I
CF3
31P NMR spectrum of compound 3n
-
S48
10 9 8 7 6 5 4 3 2 1 0 ppm
1.287
1.299
1.311
4.109
4.121
4.133
4.145
4.157
7.035
7.050
7.064
7.499
7.504
7.512
7.517
7.524
7.528
7.532
7.539
7.597
7.609
7.622
7.763
7.776
7.787
7.799
7.813
7.824
7.835
7.924
7.928
7.935
7.939
9.692
6.00
4.00
1.00
2.00
1.00
1.00
1.00
0.99
1.00
NH
OPO
EtOEtO F
Cl
1H NMR spectrum of compound 3o
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.41
16.45
63.46
63.51
116.56
116.71
119.82
119.86
121.05
121.17
122.25
124.67
125.91
130.31
130.40
130.69
130.78
132.60
132.65
132.91
132.92
135.31
135.33
139.80
139.87
154.08
155.71
166.41
166.44
NH
OPO
EtOEtO F
Cl
13C NMR spectrum of compound 3o
-
S49
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.64
NH
OPO
EtOEtO F
Cl
31P NMR spectrum of compound 3o
10 9 8 7 6 5 4 3 2 1 0 ppm
1.258
1.272
1.286
4.111
4.117
4.120
4.133
4.147
4.161
4.164
4.175
4.179
4.184
7.464
7.467
7.477
7.481
7.492
7.496
7.503
7.519
7.535
7.565
7.570
7.581
7.588
7.596
7.603
7.660
7.674
7.689
7.710
7.727
7.851
7.854
7.864
7.868
7.900
7.913
7.926
7.959
7.974
7.987
8.003
8.028
6.02
4.00
3.01
1.00
1.00
1.00
1.00
0.99
1.00
1.00
1.00
0.99
NH
OPO
EtOEtO
1H NMR spectrum of compound 3p
-
S50
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.39
16.44
63.35
63.39
120.40
121.39
124.60
125.93
126.01
126.08
126.16
126.42
127.32
128.76
130.15
130.26
130.43
130.53
132.97
133.06
133.13
134.32
140.47
140.55
167.34
167.37
NH
OPO
EtOEtO
13C NMR spectrum of compound 3p
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.87
NH
OPO
EtOEtO
31P NMR spectrum of compound 3p
-
S51
10 9 8 7 6 5 4 3 2 1 0 ppm
1.276
1.288
1.300
4.135
4.140
4.152
4.164
4.176
4.187
4.189
4.194
7.391
7.403
7.415
7.448
7.460
7.472
7.550
7.555
7.563
7.568
7.575
7.580
7.655
7.667
7.673
7.677
7.688
7.691
7.779
7.792
7.803
7.817
7.833
7.846
7.884
7.897
7.908
7.921
7.930
7.940
7.951
6.00
4.00
0.99
1.01
1.00
1.99
1.00
1.00
1.00
1.01
1.00
1.00
1.00
NH
OPO
EtOEtO
1H NMR spectrum of compound 3q
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.42
16.47
63.49
63.53
116.87
120.14
124.64
125.18
125.88
126.58
127.74
128.06
128.95
130.26
130.35
130.93
130.98
131.02
132.61
132.66
133.03
133.05
134.12
136.01
140.26
140.33
166.53
166.56
NH
OPO
EtOEtO
13C NMR spectrum of compound 3q
-
S52
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
18.02
NH
OPO
EtOEtO
31P NMR spectrum of compound 3q
10 9 8 7 6 5 4 3 2 1 0 ppm
1.252
1.264
1.276
4.104
4.113
4.116
4.129
4.141
4.153
4.157
4.164
4.169
6.995
7.003
7.007
7.014
7.015
7.020
7.547
7.551
7.552
7.560
7.563
7.565
7.572
7.576
7.578
7.609
7.621
7.634
7.706
7.709
7.722
7.732
7.735
7.975
7.988
7.999
8.011
8.120
8.126
8.128
8.136
8.145
6.01
4.00
0.99
1.00
1.00
2.00
1.00
1.00
0.99
1.00
NH
OPO
EtOEtO
N
1H NMR spectrum of compound 3r
-
S53
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.33
16.37
63.18
63.22
114.35
120.15
125.15
126.39
129.40
129.49
130.22
130.31
132.90
132.92
133.63
133.69
138.49
140.18
140.24
148.21
151.77
167.38
167.41
NH
OPO
EtOEtO
N
13C NMR spectrum of compound 3r
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.69
NH
OPO
EtOEtO
N
31P NMR spectrum of compound 3r
-
S54
10 9 8 7 6 5 4 3 2 1 0 ppm
1.164
1.176
1.188
3.967
3.979
3.991
4.005
4.017
5.860
5.876
7.114
7.130
7.131
7.148
7.174
7.178
7.185
7.189
7.192
7.199
7.203
7.304
7.318
7.329
7.339
7.526
7.528
7.531
7.533
7.539
7.540
7.544
7.546
7.551
7.553
7.557
7.559
7.609
7.611
7.622
7.632
7.635
7.677
7.686
7.687
7.698
7.936
6.00
4.00
1.00
1.00
0.98
4.01
1.00
1.00
0.98
1.00
0.97
PO
EtOEtO
NH
OPh
1H NMR spectrum of compound 3s
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.32
16.36
63.17
63.21
111.79
122.11
125.14
126.38
127.17
128.19
129.17
129.76
129.84
130.26
130.35
132.90
132.91
133.57
133.63
135.69
139.31
139.37
166.77
166.81
PO
EtOEtO
NH
OPh
13C NMR spectrum of compound 3s
-
S55
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.72
PO
EtOEtO
NH
OPh
31P NMR spectrum of compound 3s
10 9 8 7 6 5 4 3 2 1 0 ppm
1.303
1.317
1.331
3.970
4.161
4.175
4.189
4.203
4.206
4.217
4.220
7.136
7.151
7.165
7.347
7.363
7.378
7.722
7.738
7.959
7.969
7.975
7.985
8.274
8.290
8.516
8.518
8.545
8.548
9.266
6.01
3.00
4.00
1.00
2.00
2.01
1.00
1.00
0.99
0.99
NH
OPh
PO
EtOEtO
MeOOC
1H NMR spectrum of compound 3t
-
S56
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.43
16.48
52.89
63.81
63.86
120.26
124.95
125.32
126.82
129.30
131.23
131.34
131.66
131.77
133.78
133.80
133.83
133.91
138.24
143.98
144.07
165.50
165.54
165.70
165.71
NH
OPh
PO
EtOEtO
MeOOC
13C NMR spectrum of compound 3t
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.31
NH
OPh
PO
EtOEtO
MeOOC
31P NMR spectrum of compound 3t
-
S57
10 9 8 7 6 5 4 3 2 1 0 ppm
1.255
1.267
1.279
2.421
4.095
4.106
4.118
4.130
4.142
7.102
7.114
7.126
7.323
7.335
7.346
7.682
7.690
7.706
7.719
7.748
7.761
7.771
7.784
9.167
6.00
3.01
4.00
1.00
3.00
1.00
2.00
1.01
1.00
NH
OPh
PO
EtOEtO
Me
1H NMR spectrum of compound 3u
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.36
16.41
21.63
63.27
63.31
120.13
121.27
122.53
124.57
129.16
130.80
130.89
131.44
131.53
132.91
132.96
138.48
140.19
140.26
143.82
143.84
166.55
166.58
NH
OPh
PO
EtOEtO
Me
13C NMR spectrum of compound 3u
-
S58
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
18.60
NH
OPh
PO
EtOEtO
Me
31P NMR spectrum of compound 3u
10 9 8 7 6 5 4 3 2 1 0 ppm
1.254
1.266
1.278
3.869
4.081
4.086
4.089
4.093
4.098
4.101
4.110
4.113
4.122
4.126
4.134
4.138
4.143
7.006
7.010
7.014
7.020
7.024
7.029
7.107
7.120
7.132
7.326
7.339
7.352
7.397
7.402
7.405
7.409
7.713
7.726
7.791
7.805
7.814
7.828
9.277
6.01
3.00
4.00
1.00
1.00
1.99
1.00
2.00
1.00
1.00
NH
OPh
PO
EtOEtO
OMe
1H NMR spectrum of compound 3v
-
S59
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.38
16.42
55.81
63.19
63.24
115.75
115.92
116.02
116.06
116.16
117.03
120.16
124.64
129.17
134.96
135.02
138.43
142.31
142.39
163.04
163.07
166.05
166.08
NH
OPh
PO
EtOEtO
OMe
13C NMR spectrum of compound 3v
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
18.89
NH
OPh
PO
EtOEtO
OMe
31P NMR spectrum of compound 3v
-
S60
10 9 8 7 6 5 4 3 2 1 0 ppm
1.278
1.289
1.301
4.127
4.139
4.151
4.163
4.175
7.130
7.131
7.144
7.156
7.340
7.353
7.366
7.505
7.508
7.512
7.518
7.522
7.526
7.698
7.711
7.803
7.817
7.826
7.840
7.872
7.875
7.879
7.882
9.216
6.00
4.00
1.00
2.00
1.00
2.00
1.00
0.98
1.00
NH
OPh
PO
EtOEtO
Cl
1H NMR spectrum of compound 3w
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.40
16.44
63.61
63.65
120.21
123.13
124.39
124.89
129.24
130.25
130.34
131.03
131.12
134.23
134.29
138.20
139.65
139.68
141.88
141.96
164.90
164.93
NH
OPh
PO
EtOEtO
Cl
13C NMR spectrum of compound 3w
-
S61
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.90
NH
OPh
PO
EtOEtO
Cl
31P NMR spectrum of compound 3w
10 9 8 7 6 5 4 3 2 1 0 ppm
1.275
1.286
1.298
4.123
4.135
4.147
4.159
4.172
7.129
7.142
7.154
7.337
7.351
7.364
7.667
7.671
7.675
7.681
7.684
7.689
7.693
7.706
7.720
7.733
7.742
7.756
8.023
8.026
8.031
8.034
9.193
6.00
4.00
1.00
2.00
2.99
1.00
0.99
1.00
NH
OPh
PO
EtOEtO
Br
1H NMR spectrum of compound 3x
-
S62
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.41
16.45
63.65
63.69
120.22
123.59
124.85
124.92
128.12
128.14
129.26
133.28
133.38
133.89
133.98
134.21
134.28
138.18
141.80
141.88
164.80
164.83
NH
OPh
PO
EtOEtO
Br
13C NMR spectrum of compound 3x
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.03
NH
OPh
PO
EtOEtO
Br
31P NMR spectrum of compound 3x
-
S63
13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
1.329
1.341
1.352
4.107
4.119
4.124
4.133
4.136
4.145
4.148
4.150
4.157
4.162
4.174
4.187
4.199
4.202
4.211
4.216
4.223
4.228
4.239
7.097
7.098
7.109
7.122
7.294
7.303
7.311
7.324
7.337
7.350
7.545
7.549
7.554
7.558
7.792
7.805
7.806
12.118
6.01
4.01
1.00
0.99
2.00
1.00
2.00
1.00
NH
OPh
PO
EtOEtO
S
1H NMR spectrum of compound 3y
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.38
16.42
63.45
63.49
120.28
124.45
124.70
125.94
129.10
130.35
130.48
132.71
132.79
138.77
151.41
151.54
158.70
158.73
NH
OPh
PO
EtOEtO
S
13C NMR spectrum of compound 3y
-
S64
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
14.03
NH
OPh
PO
EtOEtO
S
31P NMR spectrum of compound 3y
10 9 8 7 6 5 4 3 2 1 0 ppm
3.762
3.781
7.113
7.126
7.138
7.327
7.340
7.353
7.526
7.531
7.538
7.543
7.551
7.556
7.630
7.643
7.656
7.701
7.715
7.827
7.838
7.850
7.862
7.875
9.027
6.01
0.99
2.01
1.00
1.00
2.00
2.01
1.00
NH
OPh
PO
MeOMeO
1H NMR spectrum of compound 4a
-
S65
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
53.81
53.85
120.27
123.63
124.78
124.87
129.26
130.21
130.31
130.48
130.57
132.94
133.00
133.22
133.24
138.43
140.52
140.59
166.47
166.50
NH
OPh
PO
MeOMeO
13C NMR spectrum of compound 4a
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
20.33
NH
OPh
PO
MeOMeO
31P NMR spectrum of compound 4a
-
S66
10 9 8 7 6 5 4 3 2 1 0 ppm
1.240
1.250
1.263
1.274
4.719
4.729
4.740
4.750
4.761
4.771
7.070
7.082
7.094
7.295
7.307
7.320
7.498
7.504
7.567
7.579
7.707
7.720
7.843
7.854
7.864
7.883
7.896
7.907
7.920
9.406
12.01
2.00
1.00
2.01
1.01
1.00
2.01
2.00
1.00
NH
OPh
PO
iPrO
iPrO
1H NMR spectrum of compound 4b
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
23.88
23.91
24.09
24.11
72.33
72.37
120.06
124.40
125.79
127.04
129.01
129.98
130.08
130.87
130.96
132.54
132.60
138.47
140.04
140.11
166.30
166.33
NH
OPh
PO
iPrO
iPrO
13C NMR spectrum of compound 4b
-
S67
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
15.81
NH
OPh
PO
iPrO
iPrO
31P NMR spectrum of compound 4b
10 9 8 7 6 5 4 3 2 1 0 ppm
1.253
1.263
1.387
1.398
4.722
4.733
4.743
4.746
4.754
4.756
4.766
4.777
7.100
7.112
7.125
7.303
7.311
7.320
7.329
7.342
7.355
7.529
7.532
7.537
7.541
7.800
7.812
5.99
5.99
2.00
0.99
2.99
1.01
2.00
NH
OPO
iPrO
iPrO
Ph
S
1H NMR spectrum of compound 4c
-
S68
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
23.93
23.96
24.19
24.22
72.70
72.73
120.35
124.43
126.36
127.61
129.12
130.12
130.24
133.09
133.17
138.86
150.79
150.92
158.88
158.90
NH
OPO
iPrO
iPrO
Ph
S
13C NMR spectrum of compound 4c
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
11.53
NH
OPO
iPrO
iPrO
Ph
S
31P NMR spectrum of compound 4c
-
S69
10 9 8 7 6 5 4 3 2 1 0 ppm
0.826
0.828
1.258
1.270
1.283
1.295
1.308
1.320
1.561
1.565
1.573
1.576
1.584
1.587
1.589
1.595
1.598
1.609
4.031
4.033
4.036
4.042
4.044
4.047
4.049
4.053
4.055
4.059
4.061
4.066
4.070
4.073
7.081
7.093
7.105
7.298
7.300
7.312
7.324
7.326
7.499
7.511
7.523
7.589
7.601
7.614
7.709
7.723
7.826
7.840
7.850
7.862
9.284
6.03
4.00
4.02
4.04
1.01
2.01
1.01
1.02
2.01
2.01
1.00
NH
OPh
PO
nBuO
nBuO
1H NMR spectrum of compound 4d
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.62
18.77
32.44
32.48
67.07
67.11
120.04
124.49
124.57
125.81
129.05
130.08
130.17
130.73
130.82
132.51
132.57
132.86
138.49
140.21
140.28
166.28
166.31
NH
OPh
PO
nBuO
nBuO
13C NMR spectrum of compound 4d
-
S70
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
20.33
NH
OPh
PO
nBuO
nBuO
31P NMR spectrum of compound 4d
11 10 9 8 7 6 5 4 3 2 1 0 ppm
1.199
1.211
1.223
3.913
3.917
3.924
3.929
3.936
3.941
3.953
4.087
4.099
4.103
4.111
4.115
4.123
4.128
7.100
7.112
7.125
7.311
7.324
7.337
7.388
7.394
7.401
7.407
7.414
7.420
7.460
7.462
7.464
7.473
7.475
7.485
7.487
7.530
7.531
7.542
7.543
7.555
7.556
7.591
7.604
7.616
7.619
7.628
7.631
7.678
7.691
7.702
7.711
7.723
7.886
7.894
7.898
7.906
9.698
3.00
1.00
1.01
1.00
2.00
2.02
1.00
1.01
2.01
4.00
1.00
1.00
NH
OPh
PO
EtOPh
1H NMR spectrum of compound 4f
-
S71
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.39
16.44
62.13
62.17
120.03
124.48
128.30
128.78
128.85
128.94
129.10
129.21
129.67
130.05
130.13
131.17
131.24
132.05
132.12
132.45
132.53
132.78
132.80
133.16
133.18
138.50
140.52
140.58
166.18
166.21
NH
OPh
PO
EtOPh
13C NMR spectrum of compound 4f
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
35.66
NH
OPh
PO
EtOPh
31P NMR spectrum of compound 4f
-
S72
11 10 9 8 7 6 5 4 3 2 1 0 ppm6.695
6.704
6.712
7.063
7.075
7.088
7.284
7.298
7.311
7.478
7.483
7.486
7.490
7.495
7.503
7.508
7.577
7.579
7.589
7.591
7.602
7.604
7.638
7.640
7.652
7.659
7.661
7.673
7.765
7.778
1.00
1.00
2.01
5.01
2.01
4.02
2.00
NH
OPO
PhPh
Ph
S
1H NMR spectrum of compound 4g
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
120.41
124.37
129.02
129.11
129.19
129.27
129.81
129.92
131.05
131.78
131.94
132.02
133.07
133.09
133.49
133.60
138.93
152.59
152.66
159.11
NH
OPO
PhPh
Ph
S
13C NMR spectrum of compound 4g
-
S73
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
29.27
NH
OPO
PhPh
Ph
S
31P NMR spectrum of compound 4g
11 10 9 8 7 6 5 4 3 2 1 0 ppm
7.013
7.025
7.038
7.100
7.114
7.124
7.137
7.190
7.202
7.214
7.395
7.407
7.428
7.440
7.487
7.499
7.512
7.629
7.641
7.648
7.661
7.682
8.062
8.068
8.075
8.080
10.536
1.00
0.99
2.01
7.00
2.01
5.01
1.00
1.00
NH
OPh
PO
PhPh
1H NMR spectrum of compound 4h
-
S74
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
120.12
124.14
128.54
128.68
128.76
129.32
129.97
130.12
130.20
130.82
131.55
131.61
132.24
132.30
132.42
132.83
133.21
133.28
137.90
141.32
141.37
165.42
NH
OPh
PO
PhPh
13C NMR spectrum of compound 4h
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
35.45
NH
OPh
PO
PhPh
31P NMR spectrum of compound 4h
-
S75
11 10 9 8 7 6 5 4 3 2 1 0 ppm
7.106
7.119
7.130
7.142
7.164
7.169
7.172
7.180
7.184
7.188
7.403
7.409
7.416
7.422
7.429
7.433
7.436
7.441
7.444
7.447
7.453
7.457
7.508
7.510
7.512
7.520
7.523
7.533
7.535
7.537
7.623
7.625
7.637
7.644
7.646
7.657
7.668
7.671
7.673
7.681
7.684
7.686
7.694
7.696
1.02
1.99
7.00
1.99
4.01
1.04
1.00
0.99
O
NH
POPh
PhCl
1H NMR spectrum of compound 4i
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
121.45
128.71
128.90
128.98
129.14
129.43
130.09
130.46
130.54
130.80
131.68
131.75
132.44
132.50
132.70
132.72
133.03
133.04
133.42
133.50
136.76
141.10
141.16
165.58
165.60
O
NH
POPh
PhCl
13C NMR spectrum of compound 4i
-
S76
-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
35.84
O
NH
POPh
PhCl
31P NMR spectrum of compound 4i
10 9 8 7 6 5 4 3 2 1 0 ppm
1.254
2.353
6.955
6.968
7.224
7.237
7.250
7.409
7.423
7.448
7.460
7.473
7.509
7.519
7.531
7.542
7.851
7.863
7.897
12.01
3.00
1.00
1.02
1.00
1.99
1.02
2.01
0.99
NH
O
Bpin
Me
1H NMR spectrum of compound 6a
-
S77
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
21.72
25.23
83.73
117.52
121.10
125.58
127.24
128.96
129.10
131.98
135.29
138.08
139.22
165.96
NH
O
Bpin
Me
13C NMR spectrum of compound 6a
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
1.452
7.112
7.114
7.116
7.125
7.126
7.129
7.137
7.140
7.141
7.351
7.354
7.358
7.367
7.369
7.372
7.378
7.381
7.384
7.505
7.711
7.715
7.717
7.720
7.726
7.730
7.731
10.752
11.98
0.99
2.00
1.98
1.99
1.00
NH
OPh
Bpin
S
1H NMR spectrum of compound 6b
-
S78
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
25.14
85.60
119.95
124.23
129.25
130.09
136.39
139.09
151.92
160.51
NH
OPh
Bpin
S
13C NMR spectrum of compound 6b