Modulating stereoselectivity in allylic C(sp(3))-H bond arylations via nickel and photoredox catalysis.
Modulating stereoselectivity in allylic C(sp(3))-H bond arylations via nickel and photoredox catalysis.
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DOI：
10.1038/s41467-023-36103-0
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发表时间：
2023-02-01
影响因子：
16.6
通讯作者：
Rueping, Magnus
中科院分区：
文献类型：
--
作者：
Huang, Long;Szewczyk, Marcin;Kancherla, Rajesh;Maity, Bholanath;Zhu, Chen;Cavallo, Luigi;Rueping, Magnus
虽然在自由基化学领域中开发选择性C-H键交叉偶联已经取得了重大进展，但位点和立体选择性仍然是一个长期的挑战。在这里，我们提出了成功的立体分散烯丙基C（SP3）-H键芳基化的发展，通过系统的调查的方向和程度的立体选择性的交叉耦合过程。与烯烃的光敏几何异构化反应相比，该催化反应证明了通过配体控制以及空间和电子效应来切换C-C双键立体选择性的可行性。计算研究解释了立体化学的结果，并表明，从单重态到三重态的镍-烯丙基络合物的激发的烯丙基基团的配位的自发变化的结果，随后的异构化可以通过选择的配体，以实现E/Z的选择性。烯烃中C-C双键的选择性构建是有机化学的一个基本焦点，烯烃可以是两种异构体之一。在这里，作者系统地研究了烯丙基C（sp3）-H键芳基化反应的立体选择性，并证明了配体开关可以允许立体分散合成甲硅烷基烯醇醚。
While significant progress has been made in developing selective C-H bond cross-couplings in the field of radical chemistry, the site and stereoselectivity remain a long-standing challenge. Here, we present the successful development of stereodivergent allylic C(sp3)-H bond arylations through a systematic investigation of the direction and degree of stereoselectivity in the cross-coupling process. In contrast to the signature photosensitized geometrical isomerization of alkenes, the catalytic reaction demonstrates the feasibility of switching the C-C double bond stereoselectivity by means of ligand control as well as steric and electronic effects. Computational studies explain the stereochemical outcome and indicate that excitation of a Ni-allyl complex from singlet to a triplet state results in a spontaneous change of the allyl group coordination and that the subsequent isomerization can be directed by the choice of the ligand to achieve E/Z selectivity. The selective construction of C-C double bonds in alkenes, which can be one of two isomers, is a fundamental focus of organic chemistry. Here, the authors systematically investigated the stereoselectivity in allylic C(sp3)-H bond arylations and demonstrated a ligand switch could allow a stereodivergent synthesis of silyl enol ethers.
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