Direct Formic Acid Mediated
<i>Z</i>
‐Selective Reductive Coupling of Dienes and Aldehydes
作者:Christopher Cooze、Raphael Dada、Rylan J. Lundgren
DOI:10.1002/anie.201905540
日期:2019.8.26
carbonyls to generate Z-olefin products remain rare and often require either alkyl borane or zinc reductants, limiting their utility. Demonstrated here is that formic acid mediates the Rh-catalyzed, Z-selective coupling of dienes and aldehydes. The process is distinguished by broad tolerance towards reducible or electrophilic groups. Kinetic analysis suggests that generation of the catalytically active
将不饱和亲核试剂加成羰基以生成Z-烯烃产物的方法仍然很少,并且常常需要烷基硼烷或锌还原剂,从而限制了它们的实用性。在此证明,甲酸介导Rh催化的二烯和醛的Z-选择性偶联。该方法的特点是对还原性或亲电子基团具有广泛的耐受性。动力学分析表明,通过配体离解产生催化活性的Rh中间体是决定速率的步骤。Rh-烯丙基中间体的快速生成和捕获是防止困扰相关方案的链走异构化事件的关键。通过这项研究获得的见解可能在选择性金属催化的加氢官能化反应中具有更广泛的意义。