Catalytic Enantio- and Regioselective Addition of Nucleophiles in the Intermolecular Hydrofunctionalization of 1,3-Dienes
Catalytic Enantio- and Regioselective Addition of Nucleophiles in the Intermolecular Hydrofunctionalization of 1,3-Dienes
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DOI：
10.1021/acscatal.9b04712
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发表时间：
2020-01-17
期刊：
影响因子：
12.9
通讯作者：
Malcolmson, Steven J.
中科院分区：
文献类型：
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作者：
Adamson, Nathan J.;Malcolmson, Steven J.
具有烯丙基立体中心的小分子结构单元的催化对映选择性合成是有机合成中的一个重要目标，但是在一个步骤中制备其中相邻烯烃被1，2-二取代的这种基序是一个巨大的挑战。后过渡金属催化的亲核试剂和1，3-二烯在加氢官能化反应中的分子间偶联已经迅速成为这些和相关化合物的一种引人注目的方法。在这个角度来看，我们说明了这些分子间二烯加氢官能化是如何提供了一个途径，复杂的，非常理想的化学空间，是不容易通过其他技术访问。我们还旨在提供一些洞察这些无数反应的不同机理途径和细微差别，以帮助为未来的反应和催化剂设计提供信息。
Catalytic enantioselective synthesis of small-molecule building blocks with allylic stereogenic centers is an important objective in organic synthesis, but preparing this motif wherein the adjacent olefin is 1,2-disubstituted in a single step is a tremendous challenge. Late-transition-metal-catalyzed intermolecular couplings of nucleophiles and 1,3-dienes in hydrofunctionalization reactions have quickly emerged as a compelling approach to these and related compounds. In this Perspective, we illustrate how these intermolecular diene hydrofunctionalizations have provided an avenue to complex, highly desirable chemical space that is not readily accessed by other technologies. We also aim to provide some insight into the varying mechanistic pathways and nuances of these myriad reactions to help inform future reaction and catalyst design.