Regio‐ and Diastereoselective Rhodium‐Catalyzed Allylic Substitution with Unstabilized Benzyl Nucleophiles
作者:Debasis Pal、Timothy B. Wright、Ryan O'Connor、P. Andrew Evans
DOI:10.1002/anie.202008071
日期:2021.2.8
rhodium‐catalyzed allylic substitution of challenging alkyl‐substituted secondary allylic carbonates with benzylzinc reagents, which are prepared from widely available benzyl halides. This process utilizes rhodium(III) chloride as a commercially available, high‐oxidation state and bench‐stable pre‐catalyst to provide a rare example of a regio‐ and diastereoselective allylic substitution in the absence of an
我们开发了具有高度区域选择性和非对映选择性的铑催化的具有挑战性的烷基取代的仲碳酸烯丙酯的苄基锌取代烯丙基碳酸酯,该苄基锌试剂由可广泛获得的苄基卤化物制得。该方法利用氯化铑(III)作为市售的高氧化态和稳定的预催化剂,提供了在缺乏外源配体的情况下区域和非对映选择性烯丙基取代的罕见实例。该反应可耐受电子多样性的苄基锌亲核试剂和一系列功能化和/或挑战性的脂族烯丙基亲电试剂。最后,利用铑-烯丙基中间体的构型通量性开发了一种新的非对映选择性过程,用于构建邻近的无环三元/三元立体发生中心,