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

HRID 1427752Notes

Reaction equation

HRID 1427752 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-8668ce09584c47198dc59c7466199f7d
Source dataset
uspto-grants-2015_01
Patent number
US08933015B2

Reaction notes

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