Reaction SMILES: C(=O)/C=C/C.[CH2:6]([O:8][CH:9]([O:13][CH2:14][CH3:15])/[CH:10]=[CH:11]/[CH3:12])[CH3:7].C(OCC)(OCC)OCC.[N+]([O-])([O-])=O.[NH4+]>CCO.CCOC(C)=O>[CH2:6]([O:8][CH:9]([O:13][CH2:14][CH3:15])[CH:10]=[CH:11][CH3:12])[CH3:7]
Reactant: C/C=C/C(OCC)OCC
Agent: C/C=C/C=O
Agent: O=[N+]([O-])[O-]
Agent: [NH4+]
Solvent: CCOC(C)=O
Solvent: CCO
Solvent: CCOC(OCC)OCC
Product: CC=CC(OCC)OCC
Reaction time: 22 h
Yield: 88.7 %

Procedure:
(2E)-1,1-diethoxybut-2-ene Crotonaldehyde (23.64 mL, 285.35 mmol), triethyl orthoformate (57.02 mL, 342.42 mmol) and ammonium nitrate (2.28 g, 28.54 mmol) were combined in 60 mL EtOH. After 22 h at ambient temperature, the reaction was diluted with EtOAc (60 mL) and washed with saturated sodium bicarbonate solution (40 mL). The aqueous layer was back extracted with EtOAc (20 mL). The combined organics were washed with brine (40 mL), dried over Na2SO4, filtered and concentrated in vacuo to give 36.5 g (89%) of 1,1-diethoxybut-2-ene. 1H NMR (CDCl3, 400 MHz) 5.84 (m, 1H); 5.54 (m, 1H); 4.82 (d, J=5.7 Hz, 1H); 3.64 (m, 2H); 3.49 (m, 2H); 1.73 (m, 3H); 1.21 (m, 6H). Step B. diisopropyl (4S,5S)-2-[(1E)-prop-1-enyl]-1,3-dioxolane-4,5-dicarboxylate A solution of (2E)-1,1-diethoxybut-2-ene (32.20 g, 223.27 mmol), (−)-diisopropyl D-tartrate (64.64 mL, 245.60 mmol) and pyridinium tosylate (2.24 g, 8.93 mmol) in 100 mL benzene was heated to 95° C. to distill off the solvent and EtOH produced. After 7 h at 95° C., the reaction was cooled to rt and concentrated in vacuo. Purification by normal phase chromatography (10−>30% EtOAc/hexanes) yielded 35.37 g (55%) of diisopropyl (4S,5S)-2-[(1E)-prop-1-enyl]-1,3-dioxolane-4,5-dicarboxylate as an orange oil. 1H NMR (CDCl3, 400 MHz) 6.03 (m, 1H); 5.86 (m, 2H); 5.12 (m, 2H); 4.71 (d, J=3.84 Hz, 1H); 4.63 (d, J=3.84 Hz, 1H); 1.78 (m, 3H); 1.30 (d, J=6.23 Hz, 12H); LC/MS [M+H]+=287. Step C. diisopropyl (4S,5S)-2-[(1S,2S)-2-methylcyclopropyl]-1,3-dioxolane-4,5-dicarboxylate To a −20° C. solution of intermediate diisopropyl (4S,5S)-2-[(1E)-prop-1-enyl]-1,3-dioxolane-4,5-dicarboxylate (4.10 g, 14.32 mmol) in 60 mL hexanes was added 1M diethylzinc in hexanes (42.96 mL, 42.96 mmol). Diiodomethane (6.92 mL, 85.92 mmol) was added dropwise with vigorous stirring. After 1 h at −20° C., the reaction was refrigerated at −5° C. After 17 h at −5° C., the reaction was stirred at 0° C. for an additional 5 h and then quenched with cold saturated ammonium chloride solution (100 mL) and extracted with Et2O (100 mL×3). The combined organics were washed w/aqueous sodium thiosulfate (100 mL) and brine (100 mL), filtered, dried over Na2SO4, filtered again and concentrated in vacuo. Purification by normal phase chromatography (10−>30% EtOAc/hexanes) yielded 3.85 g (89%) of diisopropyl (4S,5S)-2-[(1S,2S)-2-methylcyclopropyl]-1,3-dioxolane-4,5-dicarboxylate as a yellow oil. 1H NMR (CDCl3, 400 MHz) 5.12 (m, 2H); 4.78 (d, J=6.41 Hz, 1H); 4.66 (d, J=4.21 Hz, 1H); 4.57 (d, J=4.22 Hz, 1H); 1.30 (m, 12H); 1.09 (d, J=5.68 Hz, 3H); 0.94 (m, 2H); 0.67 (m, 1H); 0.39 (m, 1H); LC/MS [M+H]+=301. Step D. 2-methyl-N-{(1E)-[(1S,2S)-2-methylcyclopropyl]methylidene}propane-2-sulfinamide To a solution of diisopropyl (4S,5S)-2-[(1S,2S)-2-methylcyclopropyl]-1,3-dioxolane-4,5-dicarboxylate (0.450 g, 1.50 mmol) in 5 mL CH2Cl2/200 uL H2O was added p-toluenesulfonic acid (0.071 g, 0.38 mmol). Reaction heated to reflux at 50° C. After 16 h at 50° C., the reaction was cooled to rt. Water droplets sitting at the top of the reaction were removed. Copper (II) sulfate (0.507 g, 2.85 mmol) and R-(+)-tert-butanesulfinamide (0.173 g, 1.43 mmol) were added. After 5.5 h at ambient temperature, the reaction was filtered over a pad of celite. The celite was washed with CH2Cl2 (200 mL) and the filtrate concentrated in vacuo. Purification by normal phase chromatography (0−>50% EtOAc/hexanes) yielded 0.245 g (92%) of 2-methyl-N-{(1E)-[(1S,2S)-2-methylcyclopropyl]methylidene}propane-2-sulfinamide as a clear, colorless residue. 1H NMR (CDCl3, 400 MHz) 7.46 (d, J=7.69 Hz, 1H); 1.62 (m, 1H); 1.25 (m, 2H); 1.10 (m, 12H); 0.82 (m, 1H); LC/MS [M+H]+=188. Step E. 2-methyl-N-{(1S)-1-[(1S,2S)-2-methylcyclopropyl]ethyl}propane-2-sulfinamide To a −78° C. solution of 2-methyl-N-{(1E)-[(1S,2S)-2-methylcyclopropyl]methylidene}propane-2-sulfinamide (0.300 g, 1.60 mmol) in 5 mL CH2Cl2 was added 3M methylmagnesium bromide in Et2O (1.07 mL, 3.20 mmol). After 2 h at −78° C., the reaction was warmed to rt. After 1 h at ambient temperature, the reaction was quenched with saturated ammonium chloride solution (15 mL) and extracted with EtOAc (30 mL×2). The combined organics were washed with brine (15 mL), dried over Na2SO4, filtered and concentrated in vacuo. Purification by normal phase chromatography (0−>80% EtOAc/hexanes) yielded 0.224 g (69%) of -methyl-N-{(1S)-1-[(1S,2S)-2-methylcyclopropyl]ethyl}propane-2-sulfinamide as a clear, colorless residue. 1H NMR (CDCl3, 400 MHz) 2.77 (m, 1H); 1.31 (d, J=6.50 Hz, 3H); 1.21 (s, 9H); 1.03 (d, J=5.77 Hz, 3H); 0.54 (m, 3H); 0.30 (m, 1H); LC/MS [M+H]+=204. Step F. (1S)-1-[(1S,2S)-2-methylcyclopropyl]ethanaminium chloride To a 0° C. solution of 2-methyl-N-{(1S)-1-[(1S,2S)-2-methylcyclopropyl]ethyl}propane-2-sulfinamide (0.210 g, 1.03 mmol) in 4 mL MeOH was added 2M HCl in Et2O (0.52 mL, 1.03 mmol). Reaction stirred from 0° C. to rt over 18 h and then concentrated in vacuo. The resulting material was taken up in Et2O (4 mL) and concentrated in vacuo twice to give (1S)-1-[(1S,2S)-2-methylcyclopropyl]ethanaminium chloride as a white solid. 1H NMR (CDCl3, 400 MHz) 2.60 (m, 1H); 1.37 (d, J=6.59 Hz, 3H); 1.08 (d, J=6.04 Hz, 3H); 0.77 (m, 1H); 0.64 (m, 2H); 0.42 (m, 1H); LC/MS [M+H]+=100.