Negishi偶联反应
金属转移
锌酸盐
化学
偶联反应
试剂
反应性(心理学)
芳基
卤化物
催化作用
组合化学
有机化学
锌
烷基
替代医学
病理
医学
作者
D. Groß,Willem A. L. van Otterlo,Oliver Trapp,Dino Berthold
标识
DOI:10.1002/chem.202302841
摘要
The Negishi cross-coupling reactions involves the application of organozinc reagents and is a highly versatile reaction in synthetic organic chemistry. The transmetallation step plays a pivotal role in the mechanism of these types of cross-coupling reactions. In this study, mechanistic investigations are presented indicating that higher-order zincates are the transmetallating active species in Pd- and Ni-catalyzed Negishi cross-coupling reactions. These findings are supported by halide salt addition experiments and by obtaining a single X-ray crystal structure of the solid monoaryl higher-order zincate [1-NaphthylZnX3 ]2- Mg(THF)22+ . The procedure developed in this work was further applied to the synthesis of various monoaryl higher-order zincates, after which their synthetic usefulness in terms of high reactivity towards transmetallation in Negishi cross-couplings, as well as stability, was exemplified in several reactions.
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