Urea Catalyzed Construction of OxazinanesUrea Catalyzed Construction of Oxazinanes Andrea M. Hardman, Sonia S. So and Anita E. Mattson* Department of Chemistry, The Ohio State University,

Supporting Information Page 1 Page S1

Urea Catalyzed Construction of Oxazinanes Andrea M. Hardman, Sonia S. So and Anita E. Mattson*

Department of Chemistry, The Ohio State University, 88 W. 18th Ave., Columbus, OH 43210

Supplemental Section Table of Contents

1. General methods S1-S2 2. General procedure for the preparation of boronate ureas S2-S3 3. General procedure for the preparation of nitrones S3 4. Procedure for the cycloaddition of nitrocyclopropane carboxylates and nitrones S3-S9 5. General procedure for the decarboxylation of oxazinanes S9-S10 6. General reductions of oxazinanes S10-S11 7. Chirality Transfer studies S12-S13 8. Mechanism Studies S13-14 8. References S15 9. Selected NMR spectra S16-S51 General Methods: Methylene chloride was purified by passage through a bed of activated alumina.1 Purification of reaction products was carried out by flash chromatography using Aldrich 60 Å (40 - 63 µm). Analytical thin layer chromatography was performed on EMD Chemicals 0.25 µm silica gel 60-F254 plates. Visualization was accomplished with UV light and ceric ammonium molybdate stains followed by heating. Melting points (mp) were obtained on a Thermo Scientific Mel-temp apparatus and are uncorrected. Infrared spectra (IR) were obtained on a Perkin Elmer Spectrum 100R spectrophotometer. Infrared spectra for liquid products were obtained as a thin film on a NaCl disk and spectra for solid products were collected by preparing a NaBr pellet containing the title compound. Proton nuclear magnetic resonances (1H NMR) were recorded in deuterated solvents on a Bruker Avance AVIII 400 (400 MHz) spectrometer. Chemical shifts are reported in parts per million (ppm, δ) using the solvent as internal standard (CDCl3, δ 7.26 and DMSO, δ 2.50). 1H NMR splitting patterns are designated as singlet (s), doublet (d), triplet (t), or quartet (q). Splitting patterns that could not be interpreted or easily visualized are designated as multiplet (m) or broad (br). Coupling constants are reported in Hertz (Hz). Proton-decoupled carbon (13C NMR) spectra were recorded on a Bruker Avance AVIII 400 (100 MHz) spectrometer and are reported in ppm using the solvent as an internal standard (CDCl3, δ 77.0; DMSO, δ 39.5). Proton decoupled fluorine (19F NMR) spectra were recorded on a Bruker Avance AVIII 400 (376 MHz) spectrometer and are reported in ppm using

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CF3C6H5 as an external standard (-63.72). Boron spectra (11B NMR) were recorded on a Bruker Avance DPX 500 (160 MHz) or Bruker Avance AVIII 400 (128 MHz) spectrometer and are reported in ppm using BF3•OEt2 as an external standard (0.00). Electrospray mass spectra (ESI-MS) were obtained using a Bruker MicrOTOF Mass Spectrometer. Unless otherwise noted, all other commercially available reagents and solvents were purchased from Aldrich and used without further purification. Procedure for the Preparation of Boronate Urea 9a:

B

NH

NH

O

OO

MeMe

MeMe

CF3

CF3

CH3CNB

NH2

OO

MeMe

MeMe

+

N CF3

CF3

C

O

4.5 M KHF2

MeOH, 50 ºC

B

NH

NH

O

FFCF3

CF3

Synthesis of boronate urea pinacol ester:2

A flame-dried round bottom flask under N2 was charged with 2-aminophenyl boronic acid pinacol ester (600 mg, 2.74 mmol). Dry acetonitrile (30 mL) was added to create a clear and colorless solution. Last, 3,5-bis-trifluoromethylphenyl isocyanate (473 µL, 2.74 mmol) was introduced to the reaction flask dropwise by syringe. Shortly after addition

of the isocyanate, a white precipitate began to form. The reaction was allowed to stir at 23 °C for 4 h. The pure boronate urea pinacol ester was isolated as a white solid after vacuum filtration followed by washing with hexanes. The solid was dried under vacuum (83%). Rf = 0.94 (4:4:1 ethyl acetate/hexanes/methanol); mp 215.2 – 216.9 ºC; IR (NaBr) 3415, 3132, 2985, 1640, 1600, 1581, 1476, 1184, 1129 cm-1; 1H NMR (400 MHz, DMSO d6) δ 9.93 (br s, 1H); 9.19 (br s, 1H); 8.16 (s, 2H); 7.69 (s, 1H); 7.52-7.50 (m, 1H); 7.42-7.34 (m, 2H); 7.08-7.04 (m, 1H); 1.24 (s, 12H); 13C NMR (100 MHz, DMSO d6) δ 154.0, 142.2, 141.7, 134.7, 131.2 (q, J = 33 Hz, CCF3), 130.8, 123.8 (q, J = 271 Hz, CF3), 123.4, 119.7, 119.4 (d, J = 6 Hz, CF3), 155.61-155.5 (m), 83.0, 25.5 (the carbon bonded to boron was not seen due to broadening)3; 11B NMR (160 MHz, DMSO d6) δ 26.0 (br s); HRMS (ESI): Mass calculated for C21H21BF6N2O3 [M+H]+, 475.1622. Found [M+H]+, 475.1614. Synthesis of difluoroboronate urea 9a:2

9a: A flame-dried round bottom flask under N2 was charged with boronate urea pinacol ester (4.6 mmol) and freshly distilled MeOH (30 mL). Aqueous KHF2 (4.5 M, 18.4 mmol) was introduced to the reaction flask dropwise by syringe, resulting in a white heterogenous mixture, and the

reaction was heated to 50 °C. Shortly after heating, the reaction became a clear and colorless solution. After 2 h at 50 °C, the reaction was cooled to 23 °C and concentrated. The white solid was filtered and washed with water to afford the potassium trifluoroboryl urea salt (92%). The urea salt (1.95 g, 4.29 mmol) was dissolved in ethyl acetate (15 mL) and extracted twice with water (5 mL). The organic layer was dried and concentrated to afford a white solid, which was then dissolved in a minimal volume of hot acetonitrile. The solution was allowed to cool to room temperature and then placed in an ice bath. The precipitate was filtered off and the filtrate was concentrated to afford difluoroboryl urea 9a (1.23 g, 3.11 mmol, 72%) as a white powder. Rf = 0.74 (4:4:1 ethyl acetate/hexanes/methanol); mp 205.3 – 205.9 ºC; IR (NaBr) 3628, 3345, 2986, 1741, 1671, 1585, 1479, 1187, 1128 cm-1; 1H NMR (400 MHz, DMSO d6) δ 11.27 (br s,

NH

NH

OB

CF3

CF3

F F

NH

NH

OB

CF3

CF3

OO

MeMe Me

Me



1H); 10.65 (br s, 1H); 8.11 (s, 2H); 7.96 (s, 1H); 7.42-7.40 (m, 1H); 7.32-7.28 (m, 1H); 7.15-7.10 (m, 2H); 13C NMR (100 MHz, DMSO d6) δ 154.5, 138.1, 137.4, 131.5, 131.2, 130.9, 130.6, 128.2, 124.7, 123.0, 123.0 (q, J = 267 Hz, CF3), 118.4, 115.4; 11B NMR (160 MHz, DMSO d6) δ 3.63 (br s); 19F NMR (376 MHz, DMSO d6) δ –61.7 (s, 6F), –132.8 (s, 1F), –132.9 (s, 1F); HRMS (ESI): Mass calculated for C21H21BF6N2O3 [M+H]+, 419.0572. Found [M+H]+, 419.0580. General procedure for the preparation of nitrones: Nitrones were synthesized following a known procedure.4 A flame-dried 1000 mL round bottom flask containing a stirbar was charged with aldehyde (98.379 mmol), nitro compound (2.0 eq), and zinc dust (3.0 eq) in 500 mL 95% EtOH under an argon atmosphere. After the solution was cooled to 0 ºC, glacial acetic acid (6.0 eq) was added dropwise. The reaction was warmed to room temperature and stirred for 24 hours. The mixture was filtered through a Celite pad and the crude nitrone was concentrated under reduced pressure. Nitrones were purified via recrystallization. General procedure for the cycloaddition of nitrocyclopropane carboxylates and nitrones: A dry, screw-capped reaction vial containing a magnetic stir bar was charged with nitrocyclopropane carboxylate (0.136 mmol) and catalyst 9a (0.0204 mmol). The vial was fitted with a cap and septa and placed under a positive pressure of argon. Dry toluene (272 µL) was added followed immediately by a nitrone (0.203 mmol). The reaction was allowed to stir at 80 °C for 24 hours. The reaction was allowed to cool to room temperature and then was immediately purified by flash column chromatography with silica gel. Select oxazinane products were further purified by recrystallization when noted.

5a: The reaction was allowed to stir at 80 °C for 24 hours with methyl 1-nitro-2-phenylcyclopropanecarboxylate (30.0 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol), and N-benzylideneaniline oxide (40.0 mg, 0.203 mmol). The reaction was immediately purified by silica gel flash column chromatography (5:95 ethyl acetate/hexanes to 20:80 ethyl acetate/hexanes) yielding 52.3 mg of

5a (91%) as a mixture of diastereomers. The following characterization is for the mixture of diastereomers: 1H NMR (400 MHz, CDCl3) δ 7.60−7.42 (m, 10H); 7.26-7.08 (m, 11H); 6.89-6.84 (m, 1.5H); 6.07 (s, 0.5H); 5.98 (s, 1H); 5.08-5.00 (m, 1.5H); 4.01-4.01 (m, 3H); 3.54-3.54 (m, 1.5H); 3.26-3.01 (m, 3H). Recrystallization (20:80 ethyl acetate/hexanes) yielded the major diastereomer. The following characterization is for the major diastereomer: mp 187.5- 188.8 °C; FTIR (film) 3054, 2987, 1559, 1421, 1265, 1180, 739, 705 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.59−7.56 (m, 4H); 7.52-7.42 (m, 3H); 7.25-7.16 (m, 5H); 7.12-7.09 (m, 2H); 6.90-6.85 (m, 1H); 5.99 (s, 1H); 5.04 (dd, J = 11.6, 2 Hz, 1H); 4.01 (s, 3H); 3.17 (dd, J = 14, 12 Hz, 1H); 3.01 (ddd, J = 13.6, 2.4, 0.8 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 165.4, 147.6, 137.9, 132.0, 128.9, 128.9, 128.7, 128.4, 126.5, 122.4, 116.1, 93.4, 78.5, 66.6, 54.5, 32.9; HRMS (ESI): Mass calculated for C24H22N2O5 [M+Na]+, 441.1421. Found [M+Na]+, 441.1439.

NO

O2N CO2Me



A NOESY experiment was performed in an attempt to assign the relative stereochemistry of the major diastereomer (5a') and minor diastereomer (5a'') of oxazinane 5a. nOe correlations of 5a' were seen between HA/HB, HA/HE, HB/HC, HB/HD, HB/HE, HC/HD, and, HC/HE. Similar NOESY experimentation was performed with the minor diastereomer (5a'') which gave nOe correlations between HB/HC, HB/HD, and HC/HD. Based on the nOe signals it was determined that the diastereomers were epimeric at the stereogenic carbon containing the nitro group due to the fact that HE does not show a nOe with any other proton in 5a''. Therefore, we propose that the ester functionality is equatorial in 5a''. Crystal structures grown from racemic product of the major diastereomer 5a' and minor diastereomer 5a'' were obtained to confirm the relative stereochemistry.

5b: The reaction was allowed to stir at 80 °C for 24 hours with methyl 2-(4-chlorophenyl)-1-nitrocyclopropanecarboxylate (34.8 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol), and N-benzylideneaniline oxide (40.0 mg, 0.203 mmol). The reaction was immediately purified by silica gel flash column chromatography (5:95 ethyl acetate/hexanes to 20:80 ethyl

acetate/hexanes) yielding 41.3 mg of 5b (67%) as a mixture of diastereomers. The following characterization is for the mixture of diastereomers: FTIR (film) 3054, 2956, 1758, 1598, 1559, 1492, 1265, 1091, 824, 739 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.58-7.49 (m, 3H); 7.47-7.41 (m, 6H); 7.30 (s, 1.5H); 7.24-7.15 (m, 9H); 7.09-7.06 (m, 3H); 6.90-6.86 (m, 1.5H); 6.02 (s, 0.5H); 5.97 (s, 1H); 5.05-4.99 (m, 1.5H); 4.01 (s, 3H); 3.54 (s, 1.5H); 3.29-3.20 (m, 1H); 3.14-3.01 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 165.2; 164.0; 147.5; 147.5; 136.7; 136.3; 134.8; 132.5; 131.9; 130.6; 130.2; 130.0; 129.1; 129.0; 129.0; 128.8; 128.7; 128.7; 128.6; 128.5; 128.4; 128.0; 127.9; 127.7; 127.7; 127.5; 122.6; 116.2; 94.9; 93.2; 77.8; 66.7; 54.6; 53.7; 32.9; 32.8; HRMS (ESI): Mass calculated for C24H21ClN2O5 [M+Na]+, 475.1031. Found [M+Na]+, 475.1033.

5c: The reaction was allowed to stir at 80 °C for 24 hours with methyl 2-(4-bromophenyl)-1-nitrocyclopropanecarboxylate (39.4 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol), and N-benzylideneaniline oxide (40.0 mg, 0.203 mmol). The reaction was immediately purified by silica gel flash column chromatography (5:95 diethyl ether/hexanes to 20:80 diethyl

ether/hexanes) yielding 49.2 mg of 5c (73%) as a mixture of diastereomers. The following characterization is for the mixture of diastereomers: FTIR (film) 3054, 2986, 2958, 1759, 1597, 1558, 1491, 1454, 1256, 1047, 1012, 909, 738, 703 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.64−7.55 (m, 5H); 7.42-7.40 (m, 4H); 7.27-7.16 (m, 8H); 7.10-7.08 (m, 3H); 7.00-6.87 (m, 2H); 6.07 (s, 0.5H); 5.99 (s, 1H); 5.05-4.99 (m, 1H); 4.01 (s, 3H); 3.54 (s, 1.5H); 3.31-3.21 (m, 1H); 3.15-3.03 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 165.2, 164.0, 147.5, 147.5, 138.0, 137.2, 126.9, 132.0, 132.0, 131.5, 130.6, 130.2, 130.0, 129.0, 128.8, 128.7, 128.7, 128.5, 128.4, 128.1, 128.0, 128.0, 127.8, 122.9, 122.7, 116.2, 94.9, 93.2, 77.99, 66.7, 66.2, 54.6, 53.7, 53.5, 32.8, 32.8; HRMS (ESI): Mass calculated for C24H21ClN2O5 [M+Na]+, 519.0526. Found [M+Na]+, 519.0527.

NO

O2N CO2Me

Br

NO

O2N CO2Me

Cl

O

NPh

HC

HANO2

OO

HE

HE

HE

PhPhHD

HB

O

NPh

HC

HANO2

PhPhHD

HB

O

O

HE

HE HE

5a'

5a"



5d: The reaction was allowed to stir at 80 °C for 24 hours with methyl 2-(naphthalen-2-yl)-1-nitrocyclopropanecarboxylate (36.8 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol), and N-benzylideneaniline oxide (40.0 mg, 0.203 mmol). The reaction was immediately purified by silica gel flash column chromatography (5:95 ethyl acetate/hexanes to 20:80 ethyl

acetate/hexanes) yielding 64.9 mg of 5d (99%) as a mixture of diastereomers. The following characterization is for the mixture of diastereomers: 1H NMR (400 MHz, CDCl3) δ 7.99-7.89 (m, 5.8H), 7.68-7.61 (m, 4.2H), 7.57-7.53 (m, 2.7H), 7.27-7.27 (m, 1.1H), 7.24-7.12 (m, 9.4H), 6.90-6.86 (m, 1.4H), 6.11 (s, 0.4H), 6.02 (s, 1H), 5.25-5.18 (m, 1.4H), 4.03 (s, 3H), 3.55 (s, 1.2H), 3.55-3.13 (m, 3.2H). The following characterization is for a mixture that contains 91% major diastereomer: mp 132.9-135.6 °C; FTIR (film) 3059, 2956, 1758, 1558, 1492, 1453, 1265, 1062, 738, 620 cm-1; 1H NMR (400 MHz, CDCl3) δ 8.00-7.88 (m, 4.4H); 7.68 -7.61 (m, 3.3H); 7.58-7.53 (m, 2.2H); 7.24-7.11 (m, 7.6H); 6.09-6.86 (m, 1.1H); 610 (s, 0.1H); 6.02 (s, 1H); 5.24-5.18 (m, 1.1H); 4.04 (s, 3H); 3.55 (s, 0.3H); 3.31-3.24 (m, 1.1H); 3.17-3.13 (m, 1.1H); 13C NMR (100 MHz, CDCl3) δ 165.4, 164.2 147.7, 147.7, 138.7, 135.6, 135.2, 133.4, 133.3, 133.2, 130.6, 130.2, 129.6, 129.2, 129.1, 128.9. 128.7, 128.7, 128.7, 128.2, 127.8, 126.6, 126.6, 126.5, 125.5, 125.4, 124.3, 124.2, 122.4, 116.1, 95.2, 93.5, 78.5, 77.8, 66.5, 65.9, 54.5, 53.6, 32.9, 32.8, 31.5, 22.6, 21.0 14.1; HRMS (ESI): Mass calculated for C29H26N2O5 [M+Na]+, 491.1578. Found [M+Na]+, 491.1578.

5e: The reaction was allowed to stir at 80 °C for 24 hours with ethyl 1-nitro-2-(o-tolyl)cyclopropanecarboxylate (33.9 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol), and N-benzylideneaniline oxide (40.0 mg, 0.203 mmol). The reaction was immediately purified by silica gel flash column chromatography (100% hexanes to 50:50 dichloromethane/hexanes) yielding 29.8 mg of 5e

(49%) as a mixture of diastereomers. The following characterization is for the mixture of diastereomers: mp 134.0-138.0 °C; FTIR (film) 3054, 2986, 1753, 1559, 1492, 1453, 1265, 739, 704 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.70−7.61 (m, 3.4H); 7.41-7.31 (m, 3H); 7.28-7.28 (m, 1H); 7.25-7.22 (m, 3H); 7.19-7.10 (m, 5.5H); 6.89-6.85 (m, 1.2H); 6.10 (s, 0.2H); 6.23 (s, 1H); 5.24-5.18 (m, 1.2H); 4.55-4.43 (m, 2H); 3.97 (q, J = 7.2 Hz, 0.4H); 3.25-3.00 (m, 2.5H); 2.41-2.40 (m, 3.6H); 1.42 (t, J = 7.2 Hz, 3H); 1.01 (t, J = 7.2 Hz, 0.6H). 13C NMR (100 MHz, CDCl3) δ 164.7, 163.7, 147.7, 147.7, 36.6, 136.4, 135.9, 135.7, 132.6, 132.1, 130.8, 130.7, 130.5, 128.8, 128.7, 128.6, 128.6, 128.5, 128.4, 128.4, 128.3, 126.6, 126.4, 125.1, 124.9, 122.3, 116.1, 116.0, 95.2, 93.4, 75.8, 75.2, 66.9, 66.6, 63.9, 63.3, 32.4, 32.3, 19.0, 18.9, 14.1, 13.9; HRMS (ESI): Mass calculated for C25H24N2O5 [M+Na]+, 469.1734. Found [M+Na]+, 469.1749.

5f: The reaction was allowed to stir at 80 °C for 24 hours with ethyl 2-mesityl-1-nitrocyclopropanecarboxylate (37.7 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol), and N-benzylideneaniline oxide (40.0 mg, 0.203 mmol). The reaction was immediately purified by silica gel flash column chromatography (100% hexanes to 50:50 dichloromethane/hexanes) yielding

25.8 mg of 5f (40%) as a mixture of diastereomers. The following characterization is for the mixture of diastereomers: mp 161.7-166.6 °C; FTIR (film) 3054, 2986, 1754, 1597, 1558, 1491, 1421, 1265, 896, 738 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.59-7.46 (m, 0.3H); 7.53-7.51 (m,

NO

O2N CO2Et

NO

O2N CO2Et

NO

O2N CO2Me



2H); 7.24-7.15 (m, 5.6H); 7.06-7.04 (m, 2.3H); 6.90-6.84 (m, 3.6H); 6.23 (s, 0.16H); 6.16 (s, 1H); 5.38-5.31 (m, 1.2H); 4.54-4.40 (m, 2H); 4.05-3.93 (m, 0.3H); 3.29-3.18 (m, 1.2H); 3.07-3.03 (m; 0.2H); 2.85-2.81 (m, 1H); 2.49-2.47 (m, 7.1H); 2.29 (s, 3.6H); 1.40 (t, J = 7.2 Hz, 3H); 1.01 (t, J = 7.2 Hz, 0.5H). The following characterization is for the major diastereomer: 13C NMR (100 MHz, CDCl3) δ 165.4, 147.5, 137.9, 136.0, 132.3, 131.4, 130.4, 129.7, 128.7, 128.5, 128.2, 121.9, 115.5, 93.7, 78.4, 65.3, 64.0, 32.0, 21.3, 20.7, 13.9; HRMS (ESI): Mass calculated for C25H24N2O5 [M+Na]+, 497.2047. Found [M+Na]+, 497.2048.

5g: The reaction was allowed to stir at 80 °C for 24 hours with ethyl 2-mesityl-1-nitrocyclopropanecarboxylate (37.7 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol), and N-(4-methoxybenzylidene)aniline oxide (46.2 mg, 0.203 mmol). The reaction was immediately purified by silica gel flash column chromatography (100% hexanes to 50:50

dichloromethane/hexanes) yielding 52.2 mg of 5g (76%) as a mixture of diastereomers. The following characterization is for the mixture of diastereomers: 1H NMR (400 MHz, CDCl3) δ 7.50−7.44 (m, 2.5H); 7.19-7.15 (m, 2.5H); 7.05-7.05 (m, 2.5H); 6.90-6.84 (m, 4H); 6.76-6.72 (m, 2.5H); 6.17 (s, 0.3H); 6.10 (s, 1H); 5.37-5.28 (m, 1.3H); 4.53-4.39 (m, 2H); 4.06-3.94 (m, 0.6H); 3.73-3.72 (m, 3.9H); 3.28-3.18 (m, 1.3H); 3.06-3.02 (m, 0.3H); 2.82-2.79 (m, 1H); 2.48 (s, 7.9H); 2.29 (s, 4H); 1.39 (t, J = 7.2 Hz, 3H): 1.04 (t, J = 7.2 Hz, 1H). The following characterization is for the major diastereomer. mp 160.3-164.3 °C; FTIR (film) 3054, 2985, 2937, 1754, 1611, 1558, 1513, 1490, 1298, 1265, 1181, 1092, 738 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.46-7.44 (m, 2H); 7.25-7.15 (m, 2H); 7.05-7.03 (m, 2H); 6.90-6.83 (m, 3H); 6.74-6.72 (m, 2H); 6.09 (s, 1H); 5.32-5.29 (d, J = 12 Hz, 1H); 4.52-4.39 (m, 2H); 3.72 (s, 3H); 3.28-3.21 (m, 1H); 2.83-2.79 (m, 1H); 2.48 (s, 6H); 2.29 (s, 3H); 1.39 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 165.1, 159.5, 147.6, 137.8, 136.0, 131.4, 131.1, 130.4, 128.7, 124.1, 121.9, 115.5, 113.6, 93.8, 78.4, 65.0, 63.9, 55.0, 31.9, 21.4, 20.7, 13.9; HRMS (ESI): Mass calculated for C25H24N2O5 [M+Na]+, 527.2153. Found [M+Na]+, 527.2151.

5h: The reaction was allowed to stir at 80 °C for 24 hours with (23.3 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol), and N-benzylideneaniline oxide (40.0 mg, 0.203 mmol). The reaction was immediately purified by silica gel flash column chromatography (100% hexanes to 50:50 dichloromethane/hexanes) yielding 12.5 mg of 5h (25%) as a mixture of diastereomers as an oil. The

following characterization is for the mixture of diastereomers: FTIR (film) 3054, 2987, 1758, 1598, 1560, 1421, 1265, 896, 739 cm-1; 1H NMR (400 MHz, CDCl3) 7.53-7.49 (m, 2.8H); 7.20-7.14 (m, 7.4H); 7.07-7.04 (m, 2.8H); 6.88-6.84 (m, 1.4H); 6.12-6.01 (m, 1.4H), 5.95 (d, J = 1.2 Hz, 0.4H); 5.87 (s, 1H); 5.57-5.50 (m, 1.4H); 5.44-5.38 (m, 1.4H); 4.54-4.47 (m, 1.4H); 3.97 (s, 3H); 3.51 (s, 1.2H); 3.06-3.01 (m, 0.5H); 2.90-2.79 (m, 2.4H); 13C NMR (100 MHz, CDCl3) δ 165.3, 164.1, 147.6, 147.6, 134.7, 134.6, 131.9, 130.8, 130.3, 128.8, 128.7, 128.6, 128.4, 128.3, 122.5, 122.4, 118.4, 118.3, 116.2, 116.2, 94.7, 93.0, 76.8, 76.1, 66.8, 54.4, 53.5, 31.7, 31.6, 29.7; HRMS (ESI): Mass calculated for C25H24N2O5 [M+Na]+, 391.1264. Found [M+Na]+, 391.1263.

5i: The reaction was allowed to stir at 80 °C for 24 hours with methyl 1-nitro-2-phenylcyclopropanecarboxylate (30.0 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol), and N-(4-methylbenzylidene)aniline oxide (43.0 mg, 0.203

NO

O2N CO2Me

NO

O2N CO2EtMeO

NO

O2N CO2Me



mmol). The reaction was immediately purified by silica gel flash column chromatography (5:95 ethyl acetate/hexanes to 20:80 ethyl acetate/hexanes) yielding 60.1 mg of 5i (99%) as a mixture of diastereomers. The following characterization is for the mixture of diastereomers: 1H NMR (400 MHz, CDCl3) δ 7.57−7.53 (m, 2.5H); 7.50-7.42 (m, 5.5H); 7.40-7.30 (m, 1.5H); 7.21-7.15 (m, 3.5H); 7.15-7.01 (m, 5H); 6.89-6.85 (m, 1H); 6.04 (s, 0.4H); 5.93 (s, 1H); 5.07-5.00 (m, 1.2H); 4.01 (s, 3H); 3.51 (s, 1H); 3.24-3.00 (m, 3H); 2.25 (s, 1H); 2.23 (s, 3H). Recrystallization (1:3 dichloromethane/hexanes) yielded the major diastereomer. The following characterization is for the major diastereomer. mp 195.0-196.0 °C; FTIR (film) 3054, 2986, 1758, 1559, 1421, 1059, 735, 705 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.57-7.54 (m, 2H); 7.50-7.43 (m, 5H); 7.19-7.15 (m, 2H); 7.11-7.08 (m, 2H); 7.03-7.01 (m, 2H); 6.88-6.85 (m, 1H); 5.95 (s, 1H); 5.02 (dd, J = 12, 2.4 Hz, 1H); 4.00 (s, 3H); 3.18-3.12 (m, 1H); 3.04-3.00 (m, 1H); 2.23 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 165.4, 147.7, 138.6. 138.0, 130.5, 129.1, 128.9, 128.8, 128.7, 126.5, 122.3, 116.0, 93.5, 78.5, 66.4, 54.4, 32.9, 21.0; HRMS (ESI): Mass calculated for C25H24N2O5 [M+Na]+, 433.1758. Found [M+Na]+, 433.1743.

5j: The reaction was allowed to stir at 80 °C for 24 hours with methyl 1-nitro-2-phenylcyclopropanecarboxylate (30.0 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol), and N-(4-methoxybenzylidene)aniline oxide (46.2 mg, 0.203 mmol). The reaction was immediately purified by silica gel flash column chromatography (5:95 ethyl acetate/hexanes to 20:80 ethyl

acetate/hexanes) yielding 57.7 mg of 5j (95%) as a mixture of diastereomers. The following characterization is for the mixture of diastereomers: 1H NMR (400 MHz, CDCl3) δ 7.55−7.41 (m, 8H); 7.20-7.15 (m, 3H); 7.10-7.07 (m, 3H); 6.89-6.85 (m, 1H); 6.77-6.68 (m, 3H); 6.01 (s, 0.25H); 5.94 (s, 1H); 5.07-5.00 (m, 1.3H); 4.00 (m, 3H); 3.89 (s, 1H); 3.73 (s, 1H); 3.71 (3H); 3.29-3.01 (m, 3H). The following characterization is for the major diastereomer. mp 186.1-188.5 °C; FTIR (film) 3054, 2987, 1758, 1559, 1512, 1265, 1032, 896, 739 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.57-7.42 (m, 7H); 7.28-7.16 (m, 2H); 7.11−7.09 (m, 2H); 6.90-6.86 (m, 1H); 6.75-6.73 (m, 2H); 5.94 (s, 1H); 5.03 (dd, J = 12, 2.4 Hz, 1H); 4.01 (s, 3H); 3.71 (s, 3H); 3.18-3.12 (m, 1H); 3.06-3.01 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 165.4, 159.7, 147.7, 137.9, 131.9, 128.8, 128.8, 128.6, 126.4, 123.8, 122.3, 116.1, 113.7, 93.4, 78.4, 66.2, 54.9, 54.4, 32.7; HRMS (ESI): Mass calculated for C25H24N2O6 [M+Na]+, 471.1527. Found [M+Na]+, 471.1535.

5k: The reaction was allowed to stir at 80 °C for 24 hours with methyl 1-nitro-2-phenylcyclopropanecarboxylate (30.0 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol), and N-(4-chlorobenzylidene)aniline oxide (47.0 mg, 0.203 mmol). The reaction was immediately purified by silica gel flash column chromatography (5:95 ethyl acetate/hexanes to 20:80 ethyl

acetate/hexanes) yielding 53.7 mg of 5k (87%) as a mixture of diastereomers. The following characterization is for the mixture of diastereomers: 1H NMR (400 MHz, CDCl3) δ 7.55-7.44 (m, 9H); 7.36-7.32 (m, 2H); 7.22-7.16 (m, 6H); 7.09-7.07 (m, 3H); 6.92-6.88 (m, 1H); 6.05 (s, 0.5H); 5.97 (s, 1H); 5.09-5.02 (m, 1.5H); 4.01 (s, 3H); 3.58 (s, 1.3H); 3.29-3.24 (m, 0.5H); 3.13-3.00 (m, 2H); Recrystallization (hexanes) yielded the major diastereomer. The following characterization is for the major diastereomer. mp 159.5-160.1°C; FTIR (film) 3054, 2987, 1758, 1560, 1492, 1421, 1265, 1093, 739 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.54-7.44 (m, 7H); 7.25-7.17 (m, 4H); 7.09-7.06 (m, 2H); 6.92-6.87 (m, 1H); 5.96 (s, 1H); 5.03 (dd, J = 10, 4.4, Hz, 1H);

NO

O2N CO2MeMeO

NO

O2N CO2MeCl



4.01 (s, 3H); 3.09-3.07 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 165.1, 147.4, 137.6, 135.1, 131.9, 130.5, 128.9, 128.9, 128.8, 128.6, 126.4, 122.7, 166.1, 93.2, 78.4, 66.1, 54.6, 54.6, 32.7; HRMS (ESI): Mass calculated for C24H21ClN2O5 [M+Na]+, 475.1031. Found [M+Na]+, 475.1011.

5l: The reaction was allowed to stir at 80 °C for 24 hours with methyl 1-nitro-2-phenylcyclopropanecarboxylate (30.0 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol), and N-((E)-3-phenylallylidene)aniline oxide (48.4 mg, 0.203 mmol). The reaction was immediately purified by flash column chromatography with silica gel (5:95 ethyl acetate/hexanes to 20:80 ethyl

acetate/hexanes) yielding 56.3 mg of 5l (93%) as a mixture of diastereomers. The following characterization is for the mixture of diastereomers: FTIR (film) 3054, 2987, 1755, 1599, 1558, 1494, 1422, 1265, 1058, 909, 737, 650 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.54-7.40 (m, 8H); 7.29-7.27 (m, 6H); 7.25-7.22 (m, 4H); 7.16-7.14 (m, 3H); 6.99-6.95 (m, 1.5H); 6.58 (s, 0.5H); 6.54 (s, 1H); 6.47-6.37 (m, 1.5H); 5.50-5.44 (m, 1.5H); 5.07-5.01 (m, 1.5H); 4.01 (s, 3H); 3.75 (s, 1.5H) 3.25-3.20 (m, 0.5H); 3.10-3.06 (m, 1H); 2.90-2.73 (m, 1.5H); 13C NMR (100 MHz, CDCl3) δ 164.9, 164.3, 147.8, 139.0, 138.3, 138.1, 128.1, 135.7, 135.6, 128.8, 128.8, 128.7, 128.7, 128.6, 128.5, 128.4, 128.4, 128.3, 126.8, 126.7, 126.4, 126.3, 122.9, 122.9, 118.4, 117.1, 116.6, 116.6, 94.2, 93.2, 78.7, 77.9, 67.7, 67.1, 54.4, 53.9, 33.7, 33.6; HRMS (ESI): Mass calculated for C26H24N2O5 [M+Na]+, 467.1577. Found [M+Na]+, 467.1562.

5m: The reaction was allowed to stir at 80 °C for 24 hours with methyl 1-nitro-2-phenylcyclopropanecarboxylate (30.0 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol), and N-benzylidene-4-methylaniline oxide (43.1 mg, 0.203 mmol). The reaction was immediately purified by flash column chromatography with of silica gel (5:95 ethyl acetate/hexanes to 20:80 ethyl

acetate/hexanes) yielding 33.1 mg of 5m (56.3%) as a mixture of diastereomers. 1H NMR (400 MHz, CDCl3) δ 7.63-7.53 (m, 6H), 7.51-7.42 (m, 4.5H), 7.27-7.21 (m, 4H), 7.01-6.95 (m, 6H); 6.02-6.02 (m, 0.5H), 5.93 (s, 1H), 5.08-5.02 (m, 1.5H), 4.01 (s, 3H), 3.53 (s, 1.5H), 3.53-3.02 (m, 3H), 2.19, (s, 4.5H). The following characterization is for the major diastereomer. mp 181.3-183.9 °C; FTIR (film) 3054, 2987, 1759, 1558, 1454, 1422, 1265, 1059, 745, cm-1; 1H NMR (400 MHz, CDCl3) δ 7.60-7.54 (m, 4H); 7.50-7.41 (m, 3H); 7.23-7.31 (m, 3H); 7.00-6.95 (m, 4H); 5.92 (s, 1H); 5.03 (dd, J = 12, 2 Hz, 1H); 4.01 (s, 1H); 3.17-3.11 (m, 1H); 3.05-3.01 (m; 1H); 2.19 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 165.4, 145.3, 138.0, 132.2, 131.9, 130.7, 129.2, 128.8, 128.8, 128.3, 126.5, 116.3, 93.5, 78.4, 66.8, 54.5, 32.9, 20.5, 14.1; HRMS (ESI): Mass calculated for C25H24N2O5 [M+Na]+, 455.1578. Found [M+Na]+, 455.1571.

5n: The reaction was allowed to stir at 80 °C for 24 hours with methyl 1-nitro-2-phenylcyclopropanecarboxylate (30.0 mg, 0.136 mmol), catalyst 9a (8.08 mg, 0.0204 mmol) and (N-(benzo[d][1,3]dioxol-5-ylmethylene)aniline oxide (49.1 mg, 0.203 mmol). The reaction was immediately purified by silica gel flash column chromatography with

(5:95 ethyl acetate/hexanes to 20:80 ethyl acetate/hexanes) yielding 29.3 mg of 5n (47%) as a mixture of diastereomers. The following characterization is for the major diastereomer. mp 203.3-204.7 °C; FTIR (film) 3054, 2987, 1759, 1559, 1489, 1421, 1264, 1041, 898, 739 cm -1; 1H NMR (400 MHz, CDCl3) δ 7.54-7.40 (m, 5H); 7.23-7.17 (m, 3H); 7.10-7.08 (m, 2H); 6.97-

NO

O2N CO2Me

NO

O2N CO2Me

NO

O2N CO2Me

O

O



6.94 (m, 1H); 6.90-6.87 (m, 1H); 6.63-6.61 (m, 1H); 5.89-5.87 (m, 3H); 4.99 (dd, J = 12, 2 Hz, 1H); 3.99 (s, 3H); 3.17-3.10 (m, 1H); 3.03-3.00 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 165.3, 148.0, 147.6, 147.5, 137.7, 128.9, 128.7, 126.5, 126.3, 125.4, 125.0, 122.4, 116.1, 110.7, 108.1, 101.1, 93.5, 78.4, 66.2, 54.5, 32.7; HRMS (ESI): Mass calculated for C25H22N2O7 [M+Na]+, 485.1319. Found [M+Na]+, 485.1311. Procedures for the decarboxylation of oxazinane 5a to 10a:2a

To obtain a 1:2 (10a' : 10a'') mixture of diastereomers: 5a as a 2:1 mixture of diastereomers (50 mg, 0.120 mmol) was placed in a screw-capped reaction vial containing a magnetic stir bar followed by LiOH�H2O (15.1 mg, 0.360 mmol, 3.0 eq). The mixture was dissolved in 2:1 dioxanes: H2O (2.25

mL) and heated to 80 oC for 96 h. The reaction was neutralized with 3M HCl, extracted with DCM, and dried over Na2SO4. The product contained a mixture of diastereomers in a 1 to 2 ratio based on a crude 1H NMR. The product was immediately purified by silica gel column chromatography (100% hexanes to 50:50 hexanes/dichloromethane) yielding 30.6 mg (71%) of 10a as an oil. A crystal structure was obtained from racemic 10a'' to confirm the relative stereochemistry of 10a''.

To obtain a 5:1 (10a' : 10a'') mixture of diastereomers: 5a as a mixture of diastereomers (75 mg, 0.179 mmol) was placed in a round bottom flask containing a magnetic stir bar followed by LiOH�H2O (113 mg, 2.685 mmol, 15.0 eq). The mixture was dissolved in 2:1 dioxanes: H2O (3.60 mL) and heated to

100 oC for 18 h. The reaction was neutralized with 3M HCl, extracted with DCM, and dried over Na2SO4. The product contained a mixture of diastereomers in a 5 to 1 ratio based on a crude 1H NMR. The product was immediately purified by silica gel column chromatography (100% hexanes to 50:50 hexanes/dichloromethane) yielding 38.6 mg (60%) of 10a as an oil. The following characterization is for the major diastereomer 10a' (oil): FTIR (film) 3055, 2981, 1595, 1551, 1495, 1421, 1376, 1263, 895, 747 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.58-7.53 (m, 4H); 7.50-7.40 (m, 3H): 7.25-7.23 (m, 3H); 7.22-7.17 (m, 2H); 7.08-7.05 (m, 2H); 6.90-6.83 (m, 1H); 5.63 (d, J = 5.6 Hz, 1H); 5.44 (ddd, J = 12.4, 5.6, 4.4 Hz, 1H); 5.14 (dd, J = 11.6, 2 Hz, 1H); 2.83 (apparent quartet, ddd, J = 12.4 Hz, 1H); 2.47 (ddd, J = 13.2, 4.4, 2.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ147.6, 138.1, 132.7, 130.2, 128.8, 128.6, 128.4, 126.6, 122.2, 115.8, 83.6, 78.9, 63.7, 30.2; (only 14 carbons appear; overlap in aromatic region); HRMS (ESI): Mass calculated for C22H20N2O3 [M+Na]+, 383.1366. Found [M+Na]+, 383.1367. The following characterization is for the diastereomer 10a'' (pale yellow solid): mp 154.6-155.2 °C; FTIR (film) 3054, 2987, 1598, 1552, 1421, 1265, 896, 739, 705 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.63-7.61 (m, 2H); 7.48-7.36 (m, 5H): 7.34-7.30 (m, 2H); 7.28-7.26 (m, 0.7H); 7.25-7.24 (m, 0.2H); 7.22-7.17 (m, 2H); 7.05-7.02 (m, 2H); 6.90-6.85 (m, 1H); 5.96 (d, J = 1.2 Hz, 1H); 5.40 (dd, J = 11.2 Hz, 2.4 Hz, 1H); 4.94 (ddd, J = 4.8, 2.8, 2,8, 1H); 2.84 (dddd, J = 15.2, 2.8, 2.4, 1.2 Hz, 1H); 2.313 (ddd, J = 15.6, 11.6, 4.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 147.8, 139.0, 135.7, 128.8, 128.7, 128.7, 128.6, 128.5, 127.8, 126.4, 121.8, 115.2, 84.7, 77.8, 62.9, 29.9; HRMS (ESI): Mass calculated for C22H20N2O3 [M+Na]+, 383.1366. Found [M+Na]+, 383.1372.

NO

NO

10a' 10a''NO2 NO2

1:2 dr

NO

NO

10a' 10a''NO2 NO2

5:1 dr



Crystal structure of 10a'': A crystal was obtained of the racemic diastereomer of 10a'' to determine the relative configuration. The nitro group of 10a'' was found to be on the opposite side of the ring from the two aromatic rings. Due to the nitro group being trans to the two aromatic rings, this diastereomer is named 10a'' for consistency of numbering throughout this text.

Reduction of oxazinane 5a:

11a: Diastereomers of 5a (2:1 dr) (50 mg, 0.120 mg) were placed in a round bottom flask containing a magnetic stir bar, 2-propanol (0.05 M) and powdered zinc (45 eq). The flask was fitted with a septa and put under an argon atmosphere. Glacial acetic acid (66 eq) was slowly added to the flask. The mixture was stirred at room temperature for 3 hours and then quenched with

aqueous saturated sodium bicarbonate. The mixture stirred vigorously for 15 minutes. After this time, the mixture was filtered through a fritted funnel with Celite, washed with water, DCM, and MeOH to ensure isolation of all material from the crude reaction mixture. The filtrate was then extracted with DCM (3x). The organic layers were combined, dried with sodium sulfate, and the solvent removed under reduced pressure. The crude material was isolated cleanly after filtration and extraction with DCM as a pale yellow solid in 94% yield (45 mg). If necessary, 11a can be purified further by silica gel flash column chromatography (20/80 ethyl acetate/hexanes to 50/50 ethyl acetate/hexanes after treatment of silica gel with 1:5:19 triethylamine/ethyl acetate/hexanes) yielding 75% (36 mg) of 11a as a 3:1 mixture of diastereomers. Relative configuration is tentatively assigned based on J values of the 1H NMR and analysis of substrates leading to this molecule. The following characterization is for the major diastereomer: mp 172.9-176.1 °C; FTIR (film) 3413, 3055, 2987, 1715 1597, 1491, 1454, 1422, 1265, 1098, 895, 737 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.69-7.67 (m, 2H); 7.56-7.53 (m, 2H): 7.48-7.44 (m, 2H); 7.41-7.37 (m, 1H); 7.28-7.22 (m, 0.3H); 7.16-7.11 (m, 2H); 7.07-7.04 (m, 2H); 6.83-6.78 (m, 1H); 5.56 (s, 1H); 5.25 (dd, J = 12 Hz, 2.4 Hz, 1H); 5.19 (bs, 1H); 4.63 (bs, 1H); 3.94 (s, 3H); 2.75 (ddd, J = 13.6, 2.4, 0.8 Hz, 1H); 2.18 (dd, J =13.2, 12.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ173.3, 148.4, 139.5, 134.9, 130.6, 128.6, 128.5, 128.2, 128.2, 128.1, 126.3, 121.5, 115.8, 78.8, 68.5, 65.9, 53.0, 33.2; HRMS (ESI): Mass calculated for C24H24N2O4 [M+Na]+, 427.1628. Found [M+Na]+, 427.1622.

NO

HN CO2MeOH

N OH PhHHNO2

Ph

H H

Ph



Reduction of oxazinane 10a':

12a': Oxazinane 10a' (30 mg, 0.083 mmol) was placed in a 5 mL round bottom flask equipped with a magnetic stir bar, 2-propanol (0.05 M) and powdered zinc (20 eq). The flask was fitted with a septa and put under an argon atmosphere. Concentrated HCl (10 eq) was slowly added to the flask. The mixture was stirred at room temperature for 2 hours and then quenched with aqueous

saturated sodium bicarbonate. The mixture stirred vigorously for 15 minutes. After this time, the mixture was filtered through a fritted funnel with Celite, washed with water, DCM, and MeOH to ensure isolation of all material from the crude reaction mixture. The filtrate was then extracted with DCM (3x). The organic layers were combined, dried with sodium sulfate, and the solvent removed under reduced pressure to afford 12a' in 97% yield (27 mg) as an oil. Relative configuration is tentatively assigned based on J values of the 1H NMR and analysis of substrates leading to this molecule. FTIR (film) 3365, 3295, 3061, 3031, 2922, 2852, 1597, 1492, 1451, 1265, 1057, 1031, 909 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.67-7.65 (m, 2H); 7.53-7.51 (m, 2H); 7.46-7.42 (m, 2H); 7.39-7.36 (m, 1H); 7.28-7.27 (m, 1.6H); 7.23-7.19 (m, 1.3H); 7.16-7.12 (m, 2H); 7.04-7.02 (m, 2H); 6.80-6.76 (m, 1H); 5.12 (dd, J = 11.6, 2 Hz, 1H); 4.96 (d, J = 5.6 Hz, 1H); 3.78 (ddd, J = 12, 10.4, 5.2 Hz, 1H); 2.11 (ddd, J = 12.8, 4.4, 2.4 Hz, 1H); 1.94 (apparent quartet, ddd, J = 12 Hz, 1H); 1.68 (bs, 2H); 13C NMR (100 MHz, CDCl3) δ 148.8, 139.9, 135.6, 130.8, 128.6, 128.6, 128.15, 128.0, 127.5, 126.4, 120.8, 115.2, 80.5, 67.5, 50.9, 37.9; HRMS (ESI): Mass calculated for C22H22N2O5 [M+H]+, 331.1805. Found [M+H]+, 331.1803.

NO

NH2



Chirality transfer studies:

(1R,2S)-methyl 1-nitro-2-phenylcyclopropanecarboxylate (4a) was prepared as previously reported.6 HPLC (OD-H Chiralcel, 5% IPA in hexanes, 1 mL/min) tr 8.0 min (major), tr 8.9 min (minor).

5a': 5a' and 5a'' were prepared as reported. 5a' was isolated from 5a'' via crystallization (IPA/hexanes) to afford an 11:1 mixture of 5a': 5a''. Relative stereochemistry was determined by crystal structure for both 5a' and 5a''. The enantiomeric excess of 5a' and was determined by HPLC (AD-H Chiralcel, 3%

IPA in hexanes, 0.5 mL/min) tt 13.4 min (major) tr 25.2 min (minor).

CO2MeNO2

NO

O2N CO2Me

Ret. Time (min) % Area

7.868.70

49.950.1


8.139.04

94.55.5


13.0524.82

51.049.0


13.7725.67

95.84.2

NO

O2N CO2MePh

NO Ph

15 mol %Boronate Urea 9a

toluene, 80 oC, 24 h91% yield

2:1 dr92% ee

NO

O2N CO2Me

4a: 89% ee 8a 5a' 5a"

PhN

MeO2C

O

O

LiOH:H2ODioxanes:H2O N

ON

O

10a' 10a''NO2 NO2

80 oC, 96 h71% yield

1:2 dr95% ee



10a'': 10a was prepared as reported above from a mixture of 5a' and 5a'' (2:1) and isolated as a single diastereomer. Relative stereochemistry was determined by x-ray crystallographic analysis. The enantiomeric excess of 10a'' was determined by HPLC (OD-H Chiralcel, 3% IPA in hexanes, 1.0 mL/min) tr 11.7 min (minor), tr 16.6 min (major).

Mechanism studies: 5k was prepared as previously reported using enantioenriched 4a and nitrone 8d to give 5k as an enantioenriched mixture of diastereomers according to the scheme above. Major diastereomer 5k' was recrystallized (IPA) from this mixture and subjected to HPLC analysis. The major enantiomer of 5k' was determined by HPLC (AD-H Chiralcel, 3% IPA in hexanes, 0.5 mL/min) tr 16.42 min (major), tr 22.55 min (minor).

NO

O2N H


11.8316.93

49.750.3


11.6316.26

2.597.5


16.3522.44

49.4650.54

NO

O2N CO2Me4-Cl-Ph

NO Ph

15 mol %Boronate Urea 9a

toluene, 80 oC, 24 h87% yield

NO

O2N CO2Me

PhN

MeO2C

O

O

4a: 87% ee 8d 5k' 5k''Cl Cl


16.4822.65

99.940.06



A crystal structure containing one enantiomer and the major diastereomer (5k') was obtained from the initial mixture of diastereomers. The exact crystal was then tested by HPLC showing that the major enantiomer was used during the acquisition of the crystal structure and absolute configuration of 5k'. From this data, it was determined that inversion of configuration occurs during the initial ring opening of the nitrocyclopropane carboxylate. HPLC trace of crystal 5k':

Crystal structure of 5k' (two Ortep plots):


16.78 100.00

ON

Ph

H4-Cl-Ph

PhN

OH3CO

O

O

HON

Ph

Ph

NO2

CO2Me

4-Cl-Ph



References: 1 Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometal.

1996, 15, 1518-1520. 2 a) So, S. S; Auvil, T. J.; Garza, V. J.; Mattson, A. E. Org. Lett. 2012, 14, 444. b) Hughes, M.

P.; Smith, B. D. J. Org. Chem. 1997, 62, 4492. 3 Wrackmeyer, B. Modern Magnetic Resonance; Webb, G. A., Ed.; Springer: Netherlands: 2006; Part 1, pp 455-457. 4 Ganton, M.D.; Kerr, M.A. J. Org. Chem. 2004, 69, 8554. 5 Lifchits, O.; Charette, A. B. Org. Lett. 2008, 10, 2809. 6 Moreau, B.; Charette, A. B. J. Am. Chem. Soc. 2005, 127, 18014.


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

3.038

3.040

3.066

3.068

3.072

3.074

3.143

3.173

3.178

3.208

4.018

5.026

5.032

5.056

5.061

5.999

6.862

6.880

6.883

6.898

7.096

7.099

7.113

7.118

7.121

7.164

7.169

7.182

7.186

7.199

7.204

7.212

7.222

7.227

7.235

7.240

7.245

7.248

7.259

7.441

7.455

7.459

7.463

7.480

7.484

7.495

7.499

7.516

7.520

7.561

7.562

7.580

7.584

7.591

7.599

7.602

7.610

1.02

1.06

3.00

1.02

1.00

1.02

2.04

5.29

3.18

4.26

Page 16


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

32.95

54.54

66.63

78.54

93.46

116.14

122.46

126.55

128.40

128.74

128.90

128.92

130.71

132.09

137.94

147.67

165.40

Page 17


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

3.014

3.018

3.045

3.053

3.081

3.110

3.115

3.144

3.207

3.545

4.019

4.996

5.003

5.025

5.030

5.978

6.062

6.872

6.882

6.890

6.901

6.906

6.909

7.069

7.071

7.090

7.158

7.161

7.166

7.176

7.180

7.184

7.187

7.197

7.206

7.217

7.233

7.236

7.248

7.302

7.441

7.454

7.460

7.464

7.475

7.491

7.496

7.507

7.512

7.544

7.551

7.556

7.558

7.564

7.568

7.575

7.584

2.66

0.96

1.61

3.00

1.57

0.98

0.55

1.56

0.46

3.10

8.90

1.50

6.18

3.13

Page 18


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

32.85

32.91

53.71

54.64

66.74

77.84

93.27

94.97

116.20

122.63

122.67

127.51

127.76

127.90

128.01

128.45

128.56

128.69

128.73

128.78

128.83

129.00

129.08

129.12

130.05

130.27

130.64

131.91

132.59

134.81

136.38

136.70

147.50

147.54

164.09

165.28

Page 19


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

3.063

3.067

3.091

3.120

3.544

4.018

5.005

5.027

5.034

5.995

6.077

6.079

6.891

6.899

6.917

7.084

7.087

7.106

7.109

7.168

7.171

7.176

7.186

7.189

7.194

7.197

7.207

7.211

7.216

7.223

7.227

7.230

7.237

7.241

7.248

7.254

7.261

7.271

7.411

7.417

7.421

7.436

7.451

7.456

7.472

7.556

7.563

7.567

7.576

7.580

7.588

7.602

7.608

7.614

7.621

7.626

7.630

7.638

7.642

2.65

1.07

1.47

3.02

1.54

1.00

0.50

1.46

0.50

3.10

5.83

3.77

4.81

2.44

3.20

Page 20


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

32.83

32.89

53.56

53.73

54.65

66.27

66.79

77.88

93.27

94.96

116.22

122.70

122.95

127.84

128.03

128.06

128.18

128.47

128.58

128.71

128.75

128.80

129.02

130.08

130.28

130.66

131.51

132.05

132.09

136.92

137.24

138.02

147.52

147.56

164.09

165.28

Page 21


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

3.170

3.172

3.176

3.178

3.249

3.279

3.283

3.313

3.556

4.040

5.183

5.189

5.213

5.218

6.024

6.884

6.887

6.902

7.116

7.119

7.138

7.141

7.170

7.176

7.188

7.192

7.210

7.215

7.226

7.230

7.238

7.243

7.249

7.548

7.552

7.558

7.560

7.566

7.570

7.572

7.614

7.622

7.625

7.633

7.638

7.656

7.660

7.677

7.681

7.895

7.905

7.918

7.932

7.945

7.949

7.957

7.979

1.12

1.18

0.29

2.97

1.10

1.00

0.10

1.08

2.23

5.48

2.19

3.36

4.45

Page 22


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

32.81

32.90

53.67

54.59

66.19

66.71

77.87

78.59

93.53

95.18

116.19

122.46

122.51

124.22

124.36

125.43

125.57

126.19

126.29

126.56

126.62

126.68

127.80

127.99

128.03

128.24

128.44

128.55

128.64

128.72

128.76

128.77

128.95

130.06

130.38

130.75

132.11

132.79

133.22

133.39

133.44

135.21

135.55

147.70

164.25

165.43

Page 23


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

1.012

1.403

1.421

1.439

2.403

2.413

3.034

3.037

3.040

3.042

3.097

3.127

4.482

4.491

4.500

4.508

4.518

5.183

5.189

5.212

5.218

6.029

6.871

6.874

6.889

7.101

7.104

7.117

7.122

7.126

7.154

7.158

7.163

7.170

7.172

7.176

7.180

7.198

7.234

7.239

7.244

7.251

7.282

7.283

7.340

7.344

7.359

7.362

7.393

7.396

7.618

7.627

7.630

7.636

7.642

7.690

7.706

0.69

3.06

3.64

2.57

0.40

2.08

1.22

1.00

0.20

1.22

2.40

3.00

3.09

0.95

2.95

2.28

1.24

Page 24


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

13.98

14.13

18.98

19.00

32.36

32.45

63.35

63.96

66.60

66.97

75.25

75.89

93.49

95.27

116.03

116.13

122.37

124.97

125.16

126.45

126.60

128.39

128.42

128.48

128.52

128.61

128.67

128.73

128.89

130.58

130.70

130.84

132.17

132.68

135.72

135.92

136.42

136.68

147.72

147.79

163.76

164.76

Page 25


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

0.994

1.012

1.030

1.386

1.404

1.422

2.293

2.478

2.494

2.818

2.852

3.224

3.256

3.290

4.425

4.434

4.443

4.452

4.460

4.470

4.477

4.487

4.495

4.504

4.513

4.522

5.310

5.314

5.340

5.345

6.160

6.843

6.862

6.880

6.903

7.041

7.043

7.063

7.152

7.157

7.162

7.168

7.176

7.179

7.184

7.197

7.207

7.218

7.223

7.232

7.236

7.243

7.248

7.250

7.512

7.519

7.532

0.53

3.17

3.55

7.11

1.03

0.16

1.18

0.34

2.05

1.17

1.00

0.16

3.59

2.37

2.48

3.20

2.03

0.33

Page 26


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

13.92

20.76

21.38

32.05

64.00

65.39

78.46

93.79

115.51

121.93

128.27

128.59

128.78

129.77

130.40

131.40

132.36

136.04

137.91

147.54

165.04

Page 27


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

1.378

1.396

1.414

2.291

2.483

2.795

2.830

3.215

3.247

3.281

3.726

4.396

4.413

4.422

4.431

4.440

4.449

4.458

4.467

4.476

4.484

4.494

4.502

4.511

4.529

5.294

5.324

6.097

6.725

6.747

6.839

6.857

6.875

6.901

7.032

7.053

7.153

7.171

7.192

7.253

7.444

7.466

3.05

3.09

6.06

1.01

1.02

3.07

2.03

1.03

1.00

2.04

1.10

2.04

2.05

2.08

2.06

Page 28


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

13.92

20.76

21.41

31.97

55.05

63.93

65.08

78.44

93.84

113.64

115.58

121.90

124.13

128.76

130.41

131.10

131.46

136.02

137.89

147.62

159.56

165.11

Page 29


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

2.843

2.846

2.852

2.854

2.871

3.519

3.970

5.410

5.413

5.415

5.418

5.437

5.439

5.442

5.528

5.531

5.532

5.572

5.575

5.578

5.871

5.951

5.954

6.865

6.868

6.870

6.886

7.048

7.051

7.054

7.073

7.076

7.143

7.150

7.155

7.161

7.165

7.168

7.172

7.177

7.185

7.186

7.190

7.197

7.200

7.204

7.208

7.213

7.216

7.220

7.224

7.230

7.496

7.502

7.507

7.512

7.516

2.47

0.50

1.26

2.91

1.40

1.42

1.41

1.00

0.47

1.40

1.43

2.85

7.48

2.87

Page 30


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

29.70

31.61

31.75

53.59

54.46

66.84

76.12

76.82

77.21

93.07

94.74

116.23

116.27

118.36

118.48

122.46

122.50

128.30

128.42

128.65

128.70

128.89

130.39

130.82

131.95

134.62

134.77

147.66

147.69

164.19

165.32

Page 31


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

2.232

3.004

3.006

3.010

3.012

3.038

3.040

3.044

3.046

3.124

3.155

3.158

3.189

4.005

5.003

5.009

5.033

5.039

5.959

6.852

6.870

6.888

7.010

7.030

7.086

7.088

7.102

7.108

7.111

7.157

7.162

7.175

7.179

7.197

7.255

7.431

7.445

7.448

7.452

7.463

7.468

7.484

7.486

7.500

7.504

7.508

7.548

7.566

3.11

1.04

1.09

3.00

1.01

1.02

1.04

2.07

2.13

2.16

5.30

2.07

Page 32


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

21.05

32.94

54.49

66.40

77.21

78.52

93.51

116.09

122.35

126.55

128.71

128.86

128.94

129.13

130.56

138.00

138.68

147.73

165.44

Page 33


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

3.019

3.022

3.025

3.028

3.054

3.056

3.060

3.124

3.154

3.158

3.188

3.718

4.011

5.014

5.020

5.044

5.050

5.946

6.732

6.737

6.749

6.754

6.866

6.884

6.900

6.902

6.905

7.090

7.092

7.111

7.114

7.168

7.173

7.186

7.190

7.203

7.208

7.438

7.445

7.453

7.456

7.460

7.478

7.492

7.496

7.505

7.513

7.517

7.530

1.03

1.01

2.99

2.92

0.99

1.00

2.04

1.02

2.00

2.06

7.13

Page 34


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

32.79

54.45

54.99

66.24

77.17

78.43

93.46

113.73

116.12

122.37

123.88

126.48

128.68

128.82

128.84

131.93

137.95

147.72

159.75

165.41

Page 35


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

3.071

3.080

3.096

4.017

5.013

5.024

5.038

5.049

5.966

6.882

6.885

6.900

6.916

6.918

6.921

7.065

7.068

7.087

7.090

7.171

7.176

7.182

7.189

7.193

7.205

7.210

7.216

7.259

7.441

7.448

7.455

7.459

7.463

7.475

7.478

7.489

7.494

7.505

7.511

7.514

7.523

2.08

3.00

1.00

1.01

0.99

2.10

4.20

7.36

Page 36


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

32.79

54.63

66.12

76.68

77.00

77.20

77.32

78.49

93.28

116.11

122.73

126.49

128.68

128.84

128.94

128.99

130.59

131.98

135.13

137.68

147.45

165.14

Page 37


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

2.836

2.866

2.870

2.900

3.068

3.071

3.511

3.752

4.011

5.018

5.041

5.440

5.462

6.408

6.431

6.448

6.471

6.542

6.582

6.970

6.972

6.974

6.990

7.140

7.143

7.157

7.162

7.165

7.220

7.232

7.241

7.245

7.247

7.252

7.271

7.274

7.285

7.288

7.290

7.292

7.422

7.440

7.444

7.457

7.460

7.463

7.471

7.475

7.480

7.493

7.496

7.501

7.504

7.519

7.521

7.524

7.538

1.58

1.14

0.41

1.23

3.39

1.53

1.57

1.57

1.00

0.52

1.51

3.12

3.82

6.07

7.97

Page 38


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

33.63

33.73

53.95

54.43

67.16

67.70

77.98

78.75

93.20

94.28

116.60

116.65

117.16

118.45

122.92

122.97

126.37

126.49

126.77

126.87

128.36

128.44

128.49

128.55

128.61

128.72

128.76

128.80

128.86

135.65

135.72

138.10

138.19

138.35

139.07

147.89

164.31

164.99

Page 39


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

3.022

3.026

3.028

3.056

3.060

3.125

3.155

3.159

3.189

3.714

4.008

5.015

5.021

5.045

5.051

5.948

6.731

6.736

6.748

6.753

6.865

6.883

6.902

7.091

7.093

7.113

7.115

7.168

7.173

7.186

7.189

7.203

7.208

7.258

7.437

7.452

7.455

7.459

7.477

7.492

7.496

7.513

7.531

7.536

7.543

7.557

1.00

1.11

2.83

2.92

1.00

1.00

2.12

1.04

1.97

2.59

7.27

Page 40


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

32.84

54.50

55.03

66.29

78.48

93.51

113.77

116.17

122.42

123.93

126.53

128.73

128.89

131.98

138.00

147.77

159.79

165.46

Page 41


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

0.858

0.879

0.890

0.906

0.923

0.981

0.998

1.264

1.281

1.299

1.329

1.550

2.065

3.034

3.064

3.137

3.167

3.201

3.837

4.024

4.135

4.153

5.003

5.008

5.033

5.038

5.319

5.907

5.913

5.926

6.648

6.668

6.900

6.918

6.937

6.977

6.981

6.997

7.001

7.016

7.110

7.130

7.202

7.220

7.241

7.257

7.260

7.280

7.434

7.452

7.470

7.490

7.508

7.526

7.539

7.558

7.576

1.02

1.02

3.00

0.98

3.01

0.93

2.00

7.97

5.14

Page 42


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

32.77

54.53

66.24

76.70

77.02

77.22

77.34

78.48

93.51

101.16

108.11

110.70

116.11

122.47

125.01

125.43

126.39

126.52

128.77

128.91

137.79

147.54

147.61

148.00

165.36

Page 43


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

2.485

2.490

2.495

2.787

2.818

2.851

5.122

5.128

5.152

5.157

5.430

5.433

5.444

5.450

5.461

5.464

5.475

5.626

5.640

6.865

6.884

6.886

6.902

7.059

7.062

7.064

7.076

7.081

7.084

7.177

7.182

7.195

7.199

7.212

7.217

7.233

7.236

7.244

7.247

7.252

7.258

7.431

7.445

7.449

7.452

7.466

7.469

7.480

7.485

7.502

7.506

7.536

7.538

7.559

7.565

7.570

7.574

1.00

1.01

0.99

1.01

1.00

1.00

1.99

2.09

2.77

3.05

3.98

Page 44


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

30.24

63.74

78.99

83.63

115.86

122.23

126.66

128.45

128.61

128.89

130.23

132.74

138.16

147.64

Page 45


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

2.313

2.825

2.827

2.862

2.865

4.942

4.947

4.952

5.389

5.396

5.418

5.424

5.968

5.971

6.862

6.880

6.899

7.032

7.035

7.037

7.049

7.054

7.057

7.177

7.182

7.195

7.199

7.212

7.217

7.260

7.265

7.280

7.283

7.286

7.309

7.313

7.324

7.328

7.346

7.349

7.387

7.400

7.405

7.409

7.420

7.425

7.435

7.439

7.451

7.456

7.459

7.464

7.467

7.484

7.489

7.614

7.632

1.01

1.00

0.99

0.98

1.00

0.99

2.00

2.00

0.19

0.76

2.01

5.02

2.00

Page 46


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

29.90

62.94

77.87

84.71

115.24

121.83

126.44

127.88

128.54

128.67

128.72

128.79

128.86

135.79

139.04

147.83

Page 47


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

2.151

2.181

2.184

2.214

2.736

2.740

2.742

2.768

2.770

2.774

2.776

3.940

5.236

5.242

5.266

5.272

5.568

6.791

6.809

6.811

6.827

7.045

7.048

7.062

7.067

7.070

7.121

7.126

7.139

7.143

7.161

7.234

7.241

7.245

7.251

7.258

7.268

7.271

7.391

7.406

7.409

7.412

7.442

7.445

7.457

7.461

7.479

7.481

7.539

7.556

7.560

7.561

7.675

7.680

7.685

7.689

7.693

1.04

1.01

3.00

0.97

0.78

1.12

1.01

1.01

2.05

2.09

2.01

0.72

1.04

2.16

2.05

2.09

Page 48


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

33.26

53.00

65.91

68.51

78.89

115.81

121.53

126.38

128.17

128.25

128.27

128.55

128.67

130.70

134.96

139.53

148.47

173.35

Page 49


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

1.680

1.894

1.924

1.956

1.986

2.088

2.094

2.099

2.106

2.121

2.127

2.132

2.138

3.754

3.766

3.779

3.783

3.796

3.809

4.957

4.971

5.109

5.114

5.138

5.143

6.769

6.771

6.787

6.789

6.805

6.807

7.022

7.025

7.044

7.125

7.144

7.164

7.165

7.199

7.217

7.223

7.235

7.271

7.288

7.360

7.378

7.384

7.396

7.429

7.449

7.466

7.517

7.536

7.651

2.57

1.21

1.00

0.98

0.93

0.99

1.02

2.01

2.16

1.27

1.60

1.22

2.13

1.99

1.90

Page 50


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

37.93

50.94

67.51

80.50

115.20

120.88

126.49

127.53

128.09

128.15

128.62

128.66

130.86

135.61

139.93

148.85

Page 51


Documents

Urea Catalyzed Construction of OxazinanesUrea Catalyzed Construction of Oxazinanes Andrea M. Hardman, Sonia S. So and Anita E. Mattson* Department of Chemistry, The Ohio State University,