Addition of Cl2C: To (-)-O-menthyl acrylate under sonication-phase-transfer catalysis. Efficient synthesis of (+)- and (-)-(2-chlorocyclopropyl)methanol

Makoto N. Masuno; Douglas M. Young; Alexander C. Hoepker; Colin K. Skepper; Tadeusz F. Molinski

doi:10.1021/jo0480186

Addition of Cl₂C: To (-)-O-menthyl acrylate under sonication-phase-transfer catalysis. Efficient synthesis of (+)- and (-)-(2-chlorocyclopropyl)methanol

Makoto N. Masuno
, Douglas M. Young
, Alexander C. Hoepker
, Colin K. Skepper
, Tadeusz F. Molinski

Renew Institute

University of California at Davis

Research output: Contribution to journal › Article › peer-review

25 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	4162-4165
Number of pages	4
Journal	Journal of Organic Chemistry
Volume	70
Issue number	10
DOIs	https://doi.org/10.1021/jo0480186
State	Published - May 13 2005

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title = "Addition of Cl2C: To (-)-O-menthyl acrylate under sonication-phase-transfer catalysis. Efficient synthesis of (+)- and (-)-(2-chlorocyclopropyl)methanol",

abstract = "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.",

author = "Masuno, \{Makoto N.\} and Young, \{Douglas M.\} and Hoepker, \{Alexander C.\} and Skepper, \{Colin K.\} and Molinski, \{Tadeusz F.\}",

year = "2005",

month = may,

day = "13",

doi = "10.1021/jo0480186",

language = "English",

volume = "70",

pages = "4162--4165",

journal = "Journal of Organic Chemistry",

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TY - JOUR

T1 - Addition of Cl2C

T2 - To (-)-O-menthyl acrylate under sonication-phase-transfer catalysis. Efficient synthesis of (+)- and (-)-(2-chlorocyclopropyl)methanol

AU - Masuno, Makoto N.

AU - Young, Douglas M.

AU - Hoepker, Alexander C.

AU - Skepper, Colin K.

AU - Molinski, Tadeusz F.

PY - 2005/5/13

Y1 - 2005/5/13

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/18744394940

U2 - 10.1021/jo0480186

DO - 10.1021/jo0480186

M3 - Article

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AN - SCOPUS:18744394940

SN - 0022-3263

VL - 70

SP - 4162

EP - 4165

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 10

ER -

Addition of Cl₂C: To (-)-O-menthyl acrylate under sonication-phase-transfer catalysis. Efficient synthesis of (+)- and (-)-(2-chlorocyclopropyl)methanol

Abstract

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