4-Methoxybenzaldehyde → (2R,3S)-3-(4-methoxyphenyl)oxirane-2-carboxylic (1S,2R)-1-(diethylamino)-2-indanyl ester

HRID 377443Notes

Reaction equation

HRID 377443 reaction equation
CC(C)([O-])C.[K+].Cl[CH2:8][C:9]([O:11][C@@H:12]1[CH2:20][C:19]2[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=2)[C@@H:13]1[N:21]([CH2:24][CH3:25])[CH2:22][CH3:23])=[O:10].[CH3:26][O:27][C:28]1[CH:33]=[CH:32][C:31]([CH:34]=[O:35])=[CH:30][CH:29]=1>C1(C)C=CC=CC=1>[CH2:22]([N:21]([CH2:24][CH3:25])[C@H:13]1[C:14]2[C:19](=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH2:20][C@H:12]1[O:11][C:9]([C@H:8]1[C@H:34]([C:31]2[CH:32]=[CH:33][C:28]([O:27][CH3:26])=[CH:29][CH:30]=2)[O:35]1)=[O:10])[CH3:23]

Participants

5

Reactant 3

HCID 312444-MethoxybenzaldehydeHCID 10880526(1s,2r)-1-(Diethylamino)-2-indanyl chloroacetateHCID 23665647Potassium tert-butoxide

Product 1

HCID 10861851(2R,3S)-3-(4-methoxyphenyl)oxirane-2-carboxylic (1S,2R)-1-(diethylamino)-2-indanyl ester

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
25 °C

Procedure

In 5-10 min., 0.95 grams (8.5 mmol) of potassium tert-butoxide was added, in small portions, to a solution of 2.05 grams (7.3 mmol) of (1S,2R)-1-(diethylamino)-2-indanyl chloroacetate and 1.0 gram (7.3 mmol) of p-anisic aldehyde in 40 ml of toluene at 20° C. The temperature increased to 25° C. After 30 minutes' stirring the reaction was quenched using a diluted NaHCO3 solution in water. The organic layer was separated and washed with water, dried using Na2SO4 and evaporated. Yield: 2.75 grams (90%) of a yellow oil. This oil is a mixture of (2R,3S)-3-(4-methoxyphenyl)oxirane-2-carboxylic (1S,2R)-1-(diethylamino)-2-indanyl ester (diastereomeric ratio 89:11) and (2R,3S)-3-(4-methoxyphenyl)oxirane-2-carboxylic tert-butyl ester (enantiomeric excess 80%). 1H NMR (200 MHz, CDCl3): 1.02 (2*t, 6H), 2.48-2.78 (m,4H), 2.95-3.27 (m, 2H), 3.44 (d, J=2.0 Hz) and 3.48 (d, J=2.0 Hz, together 1H for major and minor diastereomers, resp.), 3.80 (s, 3H), 4.02 (d, J=2.0 Hz) and 4.07 (d, J=2.0 Hz, together 1H for minor and major diastereomers, resp.), 4.60 (d, 1H), 5.62-5.75 (m, 1H), 6.85 (d, 2H) and 7.15-7.38 (d+m, 6H). 13C NMR (50.31 MHz, CDCl3): 14.71 (q), 37.58 (t), 45.35 (t), 55.30 (q), 56.85 (d), 57.97 (d), 66.51 (d), 77.02 (d), 113.49 (d), 114.10 (d), 124.93 (d), 125.32 (d), 126.81 (d), 127.12 (d), 127.27 (d), 127.74 (s), 139.16 (s), 160.18 (s) and 168.16 (s). (2R,3S)-3-(4-Methoxyphenyl)oxirane-2-carboxylic tert-butyl ester: 1H NMR (200 MHz, CDCl3): 1.43 (s, 9H), 3.33 (d, 1H), 3.73 (s, 3H), 3.89 (d, 3H), 6.81 (d, 2H) and 7.14 (d, 2H).

Workup

  1. customwas quenched
  2. customThe organic layer was separated
  3. washwashed with water
  4. customdried
  5. customevaporated
  6. additiona mixture of (2R,3S)-3-(4-methoxyphenyl)oxirane-2-carboxylic (1S,2R)-1-(diethylamino)-2-indanyl ester (diastereomeric ratio 89:11) and (2R,3S)-3-(4-methoxyphenyl)oxirane-2-carboxylic tert-butyl ester (enantiomeric excess 80%)

Sources & evidence

ORD record
ord-4362078e1dc741c9a9c2f07babe79b4b
Source dataset
uspto-grants-2000_02
Patent number
US06025506

Reaction notes

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