(1S,3S)-3-(Hydroxymethyl)-2,2-dimethylcyclopropane-1-carboxylic acid → (1r,5s)-6,6-Dimethyl-3-oxabicyclo[3.1.0]hexan-2-one

HRID 2078489Notes

Reaction equation

HRID 2078489 reaction equation
O[CH2:2][C@H:3]1[C@H:5]([C:6]([OH:8])=[O:7])[C:4]1([CH3:10])[CH3:9]>C1(C)C=CC=CC=1>[CH3:9][C:4]1([CH3:10])[C@H:5]2[C@@H:3]1[CH2:2][O:7][C:6]2=[O:8]

Participants

3

Reactant 1

HCID 67120920(1S,3S)-3-(Hydroxymethyl)-2,2-dimethylcyclopropane-1-carboxylic acid

Product 1

HCID 11094620(1r,5s)-6,6-Dimethyl-3-oxabicyclo[3.1.0]hexan-2-one

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

From 4041 g of the resultant solution, 20.1 g of that was used, and the subsequent cis body/trans body separation operation was carried out. Into 20.1 g of this solution, a 20% sodium hydroxide aqueous solution was dropped, to adjust pH of the solution to 3. An extraction operation was repeated three times from this solution with 7.8 kg of toluene, and the resultant organic layers were combined. Then, toluene was distilled off, then, 1.49 g of a solution containing 1.17 g of 6,6-dimethyl-3-oxabicyclo[3.1.0]hexan-2-one (9.27 mmol, yield based on ethyl cis-3-acetoxymethyl-2,2-dimethylcyclopropanecarboxylate: 97.2%, (1R, 5S)-body had an optical purity of 92.8% ee) was obtained. In this toluene solution, 0.057 g (0.39 mmol) of trans-3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid was present.

Workup

  1. customthe subsequent cis body/trans body separation operation
  2. additionInto 20.1 g of this solution, a 20% sodium hydroxide aqueous solution was dropped
  3. distillationThen, toluene was distilled off
  4. addition1.49 g of a solution containing 1.17 g of 6,6-dimethyl-3-oxabicyclo[3.1.0]hexan-2-one (9.27 mmol
  5. customyield
  6. customwas obtained

Sources & evidence

ORD record
ord-3cd4ef369cbb4f6dba56385567fb7926
Source dataset
uspto-grants-2011_04
Patent number
US07928253B2

Reaction notes

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