动力学分辨率
对映选择合成
对称化
化学
电泳剂
催化作用
三氟甲基
硫化物
硫黄
基质(水族馆)
组合化学
有机化学
烷基
海洋学
地质学
作者
Deng Zhu,Tong Mu,Z.-F. Li,Hui‐Yun Luo,Ren‐Fei Cao,Xiao‐Song Xue,Zhi Min Chen
标识
DOI:10.1002/anie.202318625
摘要
An efficient catalytic asymmetric electrophilic sulfenylation reaction for the synthesis of planar-chiral sulfur-containing cyclophanes has been developed for the first time. This was achieved by using a new Lewis base catalyst and a new ortho-trifluoromethyl-substituted sulfenylating reagent. Using the substrates with low rotational energy barrier, the transformation proceeded through a dynamic kinetic resolution, and the high rotational energy barrier of the substrates allowed the reaction to undergo a kinetic resolution process. Meanwhile, this transformation was compatible with a desymmetrization process when the symmetric substrates were used. Various planar-chiral sulfur-containing cyclophanes were readily obtained in moderate to excellent yields with moderate to excellent enantioselectivities (up to 97 % yield and 95 % ee). This approach was used to synthesize pharmaceutically relevant planar-chiral sulfur-containing molecules. Density functional theory calculations showed that π-π interactions between the sulfenyl group and the aromatic ring in the substrate play a crucial role in enantioinduction in this sulfenylation reaction.
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