立体中心
对映选择合成
烯烃纤维
化学
催化作用
组合化学
配体(生物化学)
立体选择性
亲核细胞
酮
有机化学
生物化学
受体
作者
Yi-Xuan Cao,Matthew D. Wodrich,Nicolai Cramer
标识
DOI:10.1038/s41467-023-43197-z
摘要
Abstract The development of efficient and sustainable methods for the construction of carbon-carbon bonds with the simultaneous stereoselective generation of vicinal stereogenic centers is a longstanding goal in organic chemistry. Low-valent nickel(0) complexes which promote α-functionalization of carbonyls leveraging its pro-nucleophilic character in conjunction with suitable olefin acceptors are scarce. We report a Ni(0)NHC catalyst which selectively converts ketones and non-conjugated dienes to synthetically highly valuable α-allylated products. The catalyst directly activates the α-hydrogen atom of the carbonyl substrate transferring it to the olefin acceptor. The transformation creates adjacent quaternary and tertiary stereogenic centers in a highly diastereoselective and enantioselective manner. Computational studies indicate the ability of the Ni(0)NHC catalyst to trigger a ligand-to-ligand hydrogen transfer process from the ketone α-hydrogen atom to the olefin substrate, setting the selectivity of the process. The shown selective functionalization of the α-C-H bond of carbonyl groups by the Ni(0)NHC catalyst opens up new opportunities to exploit sustainable 3d-metal catalysis for a stereoselective access to valuable chiral building blocks.
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