BpCu-catalyzed cyclopropanation of olefins: A simple system that operates under homogeneous and heterogeneous conditions (Bp=dihydridobis(pyrazolyl)borate)

被引:65
作者
Diaz-Requejo, MM [1 ]
Nicasio, MC [1 ]
Perez, PJ [1 ]
机构
[1] Univ Huelva, Dept Quim & Ciencia Mat, E-21819 Huelva, Spain
关键词
D O I
10.1021/om980061u
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The complexes BpCu (1), BpCuL (L = bipy, 2; L = Ph2PCH2CH2PPh2, 3; L = PCy3, 4) and BpCuL(2) (L = py, 5; L = PPh3, 6) catalyze the cyclopropanation of olefins in moderate to high yields in the homogeneous phase. These compounds can also be used under heterogeneous conditions, when supported on silica gel. Complex 1 converts an equimolar mixture of an olefin (styrene, cis-cyclooctene,1-hexene) and ethyl diazoacetate in the corresponding cyclopropanes in high yield with no excess of olefin employed. For the heterogeneous system, the catalysts can be recovered and reused several times (6-12 cycles) up to ca. 1000 turnovers. The data available suggest the existence of a common active species: the 14-electron BpCu fragment 1. These data consist of competition experiments with para-substituted styrenes as well as kinetic studies carried out in the presence and in the absence of the alkene.
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页码:3051 / 3057
页数:7
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