Triphenylphosphine → 2,2-Dimethyl-propionic acid (2S,3S,4R,5R)-3,5-dimethoxy-2,4-dimethyl-6-oxo-hexyl ester

HRID 1895762Notes

Reaction equation

HRID 1895762 reaction equation
[CH3:1][O:2][C@H:3]([C@@H:14]([CH3:21])[C@@H:15]([O:19][CH3:20])/[CH:16]=C/C)[C@@H:4]([CH3:13])[CH2:5][O:6][C:7](=[O:12])[C:8]([CH3:11])([CH3:10])[CH3:9].[O:22]=[O+][O-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl>[CH3:1][O:2][C@H:3]([C@@H:14]([CH3:21])[C@@H:15]([O:19][CH3:20])[CH:16]=[O:22])[C@@H:4]([CH3:13])[CH2:5][O:6][C:7](=[O:12])[C:8]([CH3:9])([CH3:10])[CH3:11]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 24823OzoneHCID 866758502,2-Dimethyl-propionic acid (E)-(2S,3S,4S,5S)-3,5-dimethoxy-2,4-dimethyl-oct-6-enyl ester

Product 1

HCID 866758512,2-Dimethyl-propionic acid (2S,3S,4R,5R)-3,5-dimethoxy-2,4-dimethyl-6-oxo-hexyl ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To (2,2-Dimethyl-propionic acid (E)-(2S,3S,4S,5S)-3,5-dimethoxy-2,4-dimethyl-oct-6-enyl ester (2.0 g, 6.94 mmol) in anhydrous dichloromethane (60 ml) at −78° C., ozone was bubbled through until a pale blue colour persisted. Nitrogen was then bubbled through until the solution turned colourless. Triphenylphosphine (2.7 g, 10.4 mmol) was added and the reaction was warmed to room temperature and stirred overnight. The reaction was concentrated in vacuo and the product purified by flash chromatography (SiO2, iHex/EtOAc, 20:1 then 4:1) to afford 1.62 g (81%) as a yellow oil. 1H NMR (300 MHz, CDCl3) δ 9.51 (d, J=4.1 Hz, 1H), 4.14 (dd, J=10.8 Hz, 3.3 Hz, 1H), 4.00 (dd, J=10.8 Hz, 5.9 Hz, 1H), 3.36-3.29 (m, 2H), 3.33 (s, 3H), 3.32 (s, 3H), 1.93 (m, 2H), 1.20 (s, 9H), 0.84 (d, J=7.0 Hz, 3H), 0.78 (d, J=7.0 Hz, 3H).

Workup

  1. customNitrogen was then bubbled through until the solution
  2. concentrationThe reaction was concentrated in vacuo
  3. customthe product purified by flash chromatography (SiO2
  4. customiHex/EtOAc, 20:1 then 4:1) to afford 1.62 g (81%) as a yellow oil

Sources & evidence

ORD record
ord-48b6e1edf7434afd931529abc62662dd
Source dataset
uspto-grants-2013_08
Patent number
US08513184B2

Reaction notes

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