TIN-COPPER TRANSMETALATION - CROSS-COUPLING OF ALPHA-HETEROATOM-SUBSTITUTED ALKYLTRIBUTYLSTANNANES WITH ORGANOHALIDES

被引:133
作者
FALCK, JR [1 ]
BHATT, RK [1 ]
YE, JH [1 ]
机构
[1] UNIV TEXAS,SW MED CTR,DEPT PHARMACOL,DALLAS,TX 75235
关键词
D O I
10.1021/ja00127a010
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Copper(I), in the absence of other transition metals, catalyzes the cross-coupling of (alpha-(acyloxy)benzyl)-tributylstannanes with allylic bromides in THF in fair to good yields and with aryl/vinyl halides less efficiently or not at all. Simple (alpha-(acyloxy)alkyl)tributylstannanes react sluggishly even with allyl bromide. However, proximal thiosubstituents on either reaction partner dramatically enhance yields, reaction rates, and the variety of suitable educts. (alpha-Phthalimidoylalkyl)tributylstannanes afford protected a-amino thio esters. In contrast with the Stille reaction, copper-mediated cross-couplings of alpha-heteroatom-substituted alkyltributylstannanes proceed with complete retention of configuration via a coordinatively stabilized organocopper intermediate that can be intercepted in good yield by 1,4-conjugate addition to 2-cyclohexen-1-one.
引用
收藏
页码:5973 / 5982
页数:10
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