A FACILE SYNTHESIS OF BICYCLO[M.N.1]ALKAN-1-OLS - EVIDENCE FOR ORGANOSAMARIUM INTERMEDIATES IN THE SAMARIUM(II) IODIDE PROMOTED INTRAMOLECULAR BARBIER-TYPE REACTION

被引：152

作者：

MOLANDER, GA

MCKIE, JA

机构：

[1] Department of Chemistry and Biochemistry, University of Colorado, Boulder

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 13期

关键词：

D O I：

10.1021/jo00013a008

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.

引用

页码：4112 / 4120

页数：9

共 90 条

[31] CHEMISTRY OF ORGANOSILICON COMPOUNDS .99. CONJUGATE ADDITION OF ALLYLSILANES TO ALPHA, BETA-ENONES - NEW METHOD OF STEREOSELECTIVE INTRODUCTION OF ANGULAR ALLYL GROUP IN FUSED CYCLIC ALPHA, BETA-ENONES [J].