Chiral organometallic reagents .15. The stereochemistry of carbenoid cyclopropanation reactions

被引:57
作者
Stiasny, HC [1 ]
Hoffmann, RW [1 ]
机构
[1] UNIV MARBURG,FACHBEREICH CHEM,D-35032 MARBURG,GERMANY
关键词
alkenes; carbenoids; carbolithiations; cyclopropanations; mechanistic studies;
D O I
10.1002/chem.19950010909
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The stereochemical course of the intramolecular carbenoid cyclopropanation reaction has been studied for the epimeric carbenoids 12a and 12b. In these reactions the tert-butyldimethylsilyloxy substituent serves as an internal stereochemical reference point. It was found that 12b cyclizes rapidly at -110 degrees C in a complexation-assisted concerted process to give the bicyclo[3.1.0]hexane 16. The diastereomer 12a cyclizes more slowly at -100 degrees C to give both 16 and 17; the former is probably formed by a complexation-assisted carbolithiation pathway.
引用
收藏
页码:619 / 624
页数:6
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