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J.Am.Chem.Soc.2015,137,12800~12803过渡金属催化卡宾对σ键的插入是一类非常重要的化学转化.经典的σ键的插入反应是卡宾对X—H键(X=C,N,O等)的插入.这类插入反应一般需要铑或者铜盐作为催化剂.这些反应通常是先形成活性的金属卡宾物种,然后缺电子的卡宾碳与X—H键经历协同或分步的过程完成σ键的插入.而卡宾对于更加普遍的σ键的插入则十分罕见,这种插入反应需要经过分步的机理过程.之前北京大学化学与分子工程学院王剑波课题组报道了一例一价铑催化的卡宾对碳碳σ键的形式上的插入反应(J.Am.Chem.Soc.2014,136,3013~3015).最近他们进一步设计一类新的催化
J. Am. Chem. Soc. 2015, 137, 12800-12803 The insertion of a transition metal-catalyzed carbene into the σ bond is a very important class of chemical transformations. The classical σ bond insertion reaction is the carbene insertion of the X-H bond C, N, O, etc. Such insertion reactions generally require rhodium or copper salts as a catalyst.These reactions are usually preceded by the formation of an active metal carbene species which then undergoes synergy or division with the X-H bond The insertion of the sigma bond is completed in the step, while the insertion of the carbene for the more common sigma bond is very rare, and this insertion reaction needs to go through a step-by-step mechanism.A previous study by Wang Jianbo from Peking University’s School of Chemistry and Molecular Engineering The rhodium-catalyzed formalin insertion of the carbene on the carbon-carbon σ bond (J. Am. Chem. Soc. 2014, 136, 3013-3015). Recently they further devised a new class of catalysis