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

被引：23

作者：

Masuno, MN ^{[1
]}

Young, DM ^{[1
]}

Hoepker, AC ^{[1
]}

Skepper, CK ^{[1
]}

Molinski, TF ^{[1
]}

机构：

[1] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2005年 / 70卷 / 10期

关键词：

D O I：

10.1021/jo0480186

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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 degrees 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) similar to 1.7) suggests deprotonation of CHCl3 as the rate-limiting step.

引用

收藏

页码：4162 / 4165

页数：4

相关论文

共 16 条

[1] The use of ultrasound in industrial chemical synthesis and crystallization. 1. Applications to synthetic chemistry [J].

Cains, PW ;

Martin, PD ;

Price, CJ .

ORGANIC PROCESS RESEARCH & DEVELOPMENT, 1998, 2 (01) :34-48

[2] 2 EFFECTIVE PROCEDURES FOR THE SYNTHESIS OF TRICHLOROMETHYL KETONES, USEFUL PRECURSORS OF CHIRAL ALPHA-AMINO AND ALPHA-HYDROXY ACIDS [J].

COREY, EJ ;

LINK, JO ;

SHAO, Y .

TETRAHEDRON LETTERS, 1992, 33 (24) :3435-3438

[3]

DEHMLOW EV, 1972, LIEBIGS ANN CHEM, V758, P148

[4] Asymmetric synthesis of the chlorocyclopropane containing callipeltoside A side chain [J].

Evans, DA ;

Burch, JD .

ORGANIC LETTERS, 2001, 3 (04) :503-505

[5] TETRAMETHYLAMMONIUM SALTS - HIGHLY SELECTIVE CATALYSTS FOR THE PREPARATION OF GEM-DICHLOROCYCLOPROPANES FROM ELECTROPHILIC ALKENES AND CHLOROFORM UNDER PHASE-TRANSFER CATALYSIS CONDITIONS [J].

FEDORYNSKI, M ;

ZIOLKOWSKA, W ;

JONCZYK, A .

JOURNAL OF ORGANIC CHEMISTRY, 1993, 58 (22) :6120-6121

[6] Enantioselective preparation of 2',3'-dideoxynucleosides and their analogues from ring-expansion of cyclobutanones .2. Synthesis of 2',3'-dideoxyribosides and (1S,3R)-1-amino-3-(hydroxymethyl)cyclopentane [J].

LeeRuff, E ;

Xi, FD ;

Qie, JH .

JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (04) :1547-1550

[7] 2-PHASE REACTIONS IN CHEMISTRY OF CARBANIONS AND HALOCARBENES - USEFUL TOOL IN ORGANIC SYNTHESIS [J].

MAKOSZA, M .

PURE AND APPLIED CHEMISTRY, 1975, 43 (3-4) :439-462

[8] A SIMPLE, POWERFUL, AND EFFICIENT METHOD FOR TRANSESTERIFICATION [J].

METHCOHN, O .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1986, (09) :695-697

[9]

MOUREU C, 1921, CR HEBD ACAD SCI, V172, P1269

[10]

NADIM AM, 1992, J ORG CHEM USSR, P1419