Dimethyl Sulfide → HCID 11196278, compound

HRID 982653Notes

Reaction equation

HRID 982653 reaction equation
FC(F)(F)S([O-])(=O)=O.[CH2:9]([O:12][N:13]([C@@H:36]([C:38]([O:40][CH2:41][C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1)=[O:39])[CH3:37])[C:14]([CH2:16][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)=[O:15])[CH:10]=C.O=[O+][O-].S(C)C.C([O-])([O-])=O.[K+].[K+]>C(Cl)Cl.O>[CH2:41]([O:40][C:38](=[O:39])[C@H:36]([N:13]1[C:14](=[O:15])[CH:16]=[CH:10][CH2:9][O:12]1)[CH3:37])[C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1

Participants

7

Reactant 4

HCID 1068Dimethyl SulfideHCID 11430Potassium CarbonateHCID 24823OzoneHCID 86590982HCID 86590982, compound

Product 1

HCID 11196278HCID 11196278, compoundYield 27%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent

Procedure

A solution of (R)-N-(2-triphenylphosphonio)acetyl-N-allyloxyalanine benzyl ester trifluoromethanesulfonate (5) (6.52 g, 9.95 mmol) in CH2Cl2 (180 mL) was cooled to −76˜−78° C. and saturated with ozone (a moderate bubbling until a persistent blue color) at the same temperature with stirring. An excess of ozone was removed by bubbling N2 through the reaction mixture at −76˜−78° C. and Me2S (3.1 g, 50 mmol) was added portionwise with stirring at the same temperature. The reaction mixture was allowed to warm up to room temperature and a solution of K2CO3 (6.91 g, 50 mmol) in water (20 mL) was added. After a vigorous stirring, the reaction mixture was diluted with water (100 mL) and the organic layer was separated off and washed with water (2×30 mL) and dried over MgSO4. Removal of the solvent gave a yellow semi-solid substance, which was purified by flash chromatography (Silica Gel 60, 20% EtOAc-hexanes) to afford 0.70 g (27%) the product 7a as a colorless oil. 1H NMR (400 MHz) in CDCl3 (J, Hz): δ 1.53 (3H, d, 3J=7.3, MeCH), 4.46 (1H, dq, 2J=−15.9, 3J=3.4, 4J=1.8, OCHACH═CH), 4.56 (1H, dq, 2J=15.9, 3J=3.4, 4J=1.8, OCHBCH═CH), 5.15 (1H, d, 2J=12.4, CHAPh), 5.19 (1H, q, MeCH, 3J=7.3), 5.22 (1H, d, 2J=12.4, CHBPh), 6.04 (1H, dt, 3Jcis=10.0, 4J=1.8, CH═CHCO), 6.72 (1H, dt, 3Jcis=10.0, 3J=3.4, CH2CH═CHCO), 7.27-7.40 (5H, m, Ph). 13C (100 MHz) in CDCl3: δ 13.71, 53.57, 67.08, 67.57, 122.32, 128.02, 128.26, 128.52, 135.49, 139.67, 164.64, 170.09. IR (film), cm−1: 1745, 1675, 1214, 1189. MS (CI, isobutane), m/Z: 262 (M++1). Anal. Calcd for C14H15NO4: C, 64.4; H, 5.8; N, 5.4. Found: C, 64.3; H, 5.85; N, 5.6%.

Workup

  1. customa moderate bubbling until a persistent blue color) at the same temperature
  2. customAn excess of ozone was removed
  3. customby bubbling N2 through the reaction mixture at −76˜−78° C.
  4. stirringwith stirring at the same temperature
  5. customthe organic layer was separated off
  6. washwashed with water (2×30 mL)
  7. dry with materialdried over MgSO4
  8. customRemoval of the solvent
  9. customgave a yellow semi-solid substance, which
  10. customwas purified by flash chromatography (Silica Gel 60, 20% EtOAc-hexanes)

Sources & evidence

ORD record
ord-aae7bd18bfcc4fb7b4875070d9297f9c
Source dataset
uspto-grants-2005_03
Patent number
US06861416B2

Reaction notes

Loading…