Addition of Cl2C:  to (−)-O-Menthyl Acrylate under Sonication−Phase-Transfer Catalysis. Efficient Synthesis of (+)- and (−)-(2-Chlorocyclopropyl)methanol

Dichlorocyclopropanation of (−)-O-menthyl acrylate under conditions of phase-transfer catalysis (CHCl3, KOH, tetramethylammonium bromide), with sonication, gives excellent yields (85−94%) of the corresponding dichlorocyclopropanecarboxylate ester compared to thermal conditions (90 °C, 56%). No diast...

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Bibliographic Details
Published in:Journal of organic chemistry 2005-05, Vol.70 (10), p.4162-4165
Main Authors: Masuno, Makoto N, Young, Douglas M, Hoepker, Alexander C, Skepper, Colin K, Molinski, Tadeusz F
Format: Article
Language:English
Subjects:
Acrylates - chemistry
Alicyclic compounds
Alicyclic compounds, terpenoids, prostaglandins, steroids
Catalysis
Chemistry
Cyclopropanes - chemistry
Exact sciences and technology
Hydrocarbons, Chlorinated - chemistry
Methanol - analogs & derivatives
Methanol - chemistry
Organic chemistry
Preparations and properties
Sonication
Stereoisomerism
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Summary:Dichlorocyclopropanation of (−)-O-menthyl acrylate under conditions of phase-transfer catalysis (CHCl3, KOH, tetramethylammonium bromide), with sonication, gives excellent yields (85−94%) of the corresponding dichlorocyclopropanecarboxylate ester compared to thermal conditions (90 °C, 56%). No diastereoselectivity was observed, but one isomer was isolated pure by fractional crystallization. The measured kinetic isotope effect (initial rate (CHCl3)/rate (CDCl3) ∼1.7) suggests deprotonation of CHCl3 as the rate-limiting step.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo0480186