CONSTRUCTION OF A STERICALLY CONGESTED CARBON FRAMEWORK VIA 5-HEXENYLLITHIUM CYCLIZATION - SYNTHESIS OF (+/-)-CUPARENE

被引：32

作者：

BAILEY, WF

KHANOLKAR, AD

机构：

[1] Department of Chemistry, University of Connecticut, Storrs

来源：

TETRAHEDRON | 1991年 / 47卷 / 37期

关键词：

D O I：

10.1016/S0040-4020(01)81931-1

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The naturally occurring sesquiterpene (+/-)-cuparene [1,1,2-trimethyl-2-(4-methylphenyl)cyclopentane], which contains two contiguous quaternary centers, is produced in good yield by 5-exo-trig cyclization of the 5-hexenyllithium (2) generated from 6-iodo-3,3-dimethyl-2-(4-methylphenyl)-1-hexene (3) by low temperature lithium - iodine exchange. In contrast, radical mediated cyclization of 3 proceeds via the 6-endo-trig mode to give 1,1-dimethyl-2-(4-methylphenyl)cyclohexane.

引用

收藏

页码：7727 / 7738

页数：12

相关论文

共 26 条

[1] FORMATION OF A TRANS-BICYCLO[3.3.0]OCTANE BY TANDEM ANIONIC CYCLIZATION - EVIDENCE FOR THE HIGHLY STEREOSELECTIVE IRREVERSIBLE NATURE OF 5-HEXEN-1-YLLITHIUM CYCLIZATIONS [J].

BAILEY, WF ;

KHANOLKAR, AD .

TETRAHEDRON LETTERS, 1990, 31 (42) :5993-5996

[2] PREPARATION OF 1-SUBSTITUTED BICYCLO[2.2.1]HEPTANES BY ANIONIC CYCLIZATION OF A 5-HEXEN-1-YLLITHIUM [J].

BAILEY, WF ;

KHANOLKAR, AD .

JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (24) :6058-6061

[3] CYCLIZATION OF 5-HEXENYLLITHIUM TO (CYCLOPENTYLMETHYL)LITHIUM [J].

BAILEY, WF ;

PATRICIA, JJ ;

DELGOBBO, VC ;

JARRET, RM ;

OKARMA, PJ .

JOURNAL OF ORGANIC CHEMISTRY, 1985, 50 (11) :1999-2000

[4] PREPARATION AND REGIOSPECIFIC CYCLIZATION OF ALKENYLLITHIUMS [J].

BAILEY, WF ;

NURMI, TT ;

PATRICIA, JJ ;

WANG, W .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (08) :2442-2448

[5] CONVENIENT GENERAL-METHOD FOR THE PREPARATION OF PRIMARY ALKYLLITHIUMS BY LITHIUM IODINE EXCHANGE [J].

BAILEY, WF ;

PUNZALAN, ER .

JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (19) :5404-5406

[6] TANDEM ANIONIC CYCLIZATION APPROACH TO POLYCARBOCYCLIC PRODUCTS [J].

BAILEY, WF ;

ROSSI, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (02) :765-766

[7]

BAILEY WF, 1991, IN PRESS J AM CHEM S

[8] REGIO-SELECTIVITY AND STEREO-SELECTIVITY IN RADICAL REACTIONS [J].

BECKWITH, ALJ .

TETRAHEDRON, 1981, 37 (18) :3073-3100

[9]

BIRD CW, 1974, SYNTHESIS-STUTTGART, P27

[10] REDUCTIVE LITHIATION MEDIATED ANIONIC CYCLIZATIONS AND [2,3]-SIGMATROPIC REARRANGEMENTS [J].

BROKA, CA ;

SHEN, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (08) :2981-2984