Alkene Isomerization through Allylmetals as a Strategic Tool in Stereoselective Synthesis
Alkene Isomerization through Allylmetals as a Strategic Tool in Stereoselective Synthesis
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DOI：
10.1021/acscatal.0c01174
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发表时间：
2020-05-15
期刊：
影响因子：
12.9
通讯作者：
Marek, Ilan
中科院分区：
文献类型：
--
作者：
Massad, Itai;Marek, Ilan
烯烃的位置异构化是由各种过渡金属配合物介导的众所周知的过程。然而，具有完全区域和立体选择性的烯烃异构化体系是罕见的。大多数报道的情况下，通过1，3-氢移位（烯丙基）机制，而不是一般更常见的1，2-氢化物移位（烷基）机制，引发了对前一种机制提供的独特机会的考虑。因此，这篇透视文章的第一部分将涵盖立体选择性烯烃异构化系统通过1，3-氢转移机制，重点是立体控制的起源。接下来，将讨论这些系统与随后的转化串联使用以快速形成复杂分子结构的实例，说明烯烃异构化作为立体选择性合成中的战略工具的潜力。
The positional isomerization of alkenes is a well-known process mediated by various transition metal complexes. Nevertheless, systems which isomerize alkenes with complete regio-and stereoselectivity are rare. Most reported cases proceed through 1,3-hydrogen shift (allyl) mechanisms, rather than the generally more common 1,2-hydride shift (alkyl) mechanism, provoking consideration of the unique opportunities the former mechanism offers. Accordingly, the first part of this Perspective article will cover stereoselective alkene isomerization systems operating through 1,3-hydrogen shift mechanisms, with an emphasis on the origin of stereocontrol. Next, examples where these systems are employed in tandem with subsequent transformations to rapidly form complex molecular architecture will be discussed, illustrating the potential of alkene isomerization as a strategic tool in stereoselective synthesis.