Pd-Catalyzed Olefin Functionalization Reactions for Organic Synthesis

描述（由申请人提供）：烯烃是合成中特别有吸引力的官能团。新发现的和显著改进的烯烃官能化反应可以对靶向合成的效率产生直接影响。因此，开发选择性、实用的烯烃官能化反应是学术界和工业界化学家面临的持续挑战。在该提案中，我们的目标是利用Pd（II）催化及其促进烯烃亲核加成反应和交叉偶联过程以在烯烃框架上形成多个新的C-C，C-H或C-X键的能力的烯烃官能化反应的新集合。这种反应方法的发展是再加上仔细的机理研究，其目的是阐明的基本特征，控制反应的结果，以及刺激新的反应开发和催化剂设计。目前的建议是针对开发新的Pd催化的烯烃官能化反应，使用氧化和经典的方法来产生Pd-烷基中间体。本文所述的反应开发集中于两个重要目标：A）通过使用创新方法使最初衍生自烯烃的Pd-烷基中间体官能化，（目的1和2），和B）利用我们最近开发的电子非偏置烯烃的Heck反应来获得重要的手性结构单元，同时也探讨了决定选择性钯氢化物插入和？氢化物消除（目标3）。

DESCRIPTION (provided by applicant): Alkenes are exceptionally attractive functional groups for synthesis. Newly discovered and significantly improved alkene functionalization reactions can have a direct impact on the efficiency of targeted synthesis. Therefore, the development of selective, practical alkene functionalization reactions is a continuing challenge facing chemists in both academia and industry. In this proposal, we target a new collection of alkene functionalization reactions that exploit Pd(II)-catalysis and its ability to promote both alkene nucleophilic addition reactions and cross-coupling processes to form multiple new C-C, C-H, or C-X bonds across the alkene framework. This reaction method development is coupled to careful mechanistic studies, which are designed to elucidate the fundamental features governing reaction outcomes, as well as to stimulate new reaction development and catalyst design. The current proposal is directed toward the development of new Pd-catalyzed olefin functionalization reactions using both oxidative and classical methods to generate Pd-alkyl intermediates. The reaction development described herein is focused on two significant goals: A) enabling new mechanistically-derived tactics for molecule synthesis by using innovative approaches to functionalize Pd-alkyl intermediates originally derived from an alkene (Aims 1 & 2), and B) exploiting our recently developed Heck reactions of electronically non-biased olefins to access important chiral building blocks, while also probing the factors that govern selective Pd-hydride insertion and ?-hydride elimination (Aim 3).