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钯催化肟与烷氧基丙二烯的不对称加成实现手性O,O-缩醛的合成

Access to Chiral O,O-Acetals Enabled by Palladium-Catalyzed Asymmetric Addition of Oximes to Alkoxyallenes.

作者信息

Xu Zhuo-Wei, Wang Shaozhong

机构信息

State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, 163 Xianlin Avenue, 210023, Nanjing, Jiangsu, China.

出版信息

Chemistry. 2023 Nov 21;29(65):e202301883. doi: 10.1002/chem.202301883. Epub 2023 Oct 13.

DOI:10.1002/chem.202301883
PMID:37653541
Abstract

Enantiomerically pure acyclic O,O-acetal compounds (up to 97 % ee) have been accessed through chemo-, regio- and enantioselective palladium-catalyzed addition of oximes to alkoxyallenes. DFT calculations support that a protonative hydropalladation pathway is favourable, in which the hydrogen bonding interaction between the amide group of the diphosphine ligand and the alkoxyallene is critical for the highly stereoselective formation of the dioxygenated stereogenic center.

摘要

通过化学、区域和对映选择性钯催化肟与烷氧基丙二烯的加成反应,已获得对映体纯的无环O,O - 缩醛化合物(对映体过量高达97%)。密度泛函理论计算表明,质子化氢钯化途径是有利的,其中二膦配体的酰胺基团与烷氧基丙二烯之间的氢键相互作用对于双氧化立体中心的高立体选择性形成至关重要。

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