Higher-Order Zincates as Transmetalators in Alkyl-Alkyl Negishi Cross-Coupling

Higher-Order Zincates as Transmetalators in Alkyl-Alkyl Negishi Cross-Coupling
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DOI:
10.1002/anie.201203547
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发表时间:
2012-01-01
影响因子:
16.6
通讯作者:
Organ, Michael G.
Organ, Michael G.
中科院分区:
化学1区
文献类型:
--
作者:
McCann, Lucas C.;Hunter, Howard N.;Organ, Michael G.

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根岸重述:高阶烷基锌酸盐已受到根岸偶联与烷基溴化物。这是第一次在没有盐添加剂和高介电共溶剂的情况下,在直接THF中进行耦合。这提供了证据,证明是高阶锌酸盐经过金属转化为Pd,而不是单阴离子锌酸盐或任何其他存在于施伦克平衡中的物质。
Negishi revisited: higher-order alkyl zincates have been subjected to Negishi coupling with alkyl bromides. For the first time, coupling takes place in straight THF, ie, without a salt additive and a high dielectric co-solvent. This provides evidence that it is the higher-order zincate that undergoes transmetalation to Pd, and not mono-anionic zincates or any of the other species present in the Schlenk equilibrium.