硅氢加成
对映选择合成
化学
齿合度
铜
催化作用
药物化学
戒指(化学)
立体化学
键裂
硅烷化
有机化学
金属
作者
Keisuke Sekine,Dai Akaishi,Kakeru Konagaya,Shigekazu Ito
标识
DOI:10.1002/chem.202200657
摘要
Optically active cyclopropanes have been widely investigated especially from the views of pharmaceutical and agrochemical industries, and substituting one of the methylenes with the difluoromethylene unit should be promising for developing novel biologically relevant compounds and functional materials. In this paper, the copper-catalyzed enantioselective hydrosilylation of gem-difluorocyclopropenes to provide the corresponding chiral gem-difluorocyclopropanes is presented. The use of copper(I) chloride, chiral ligands including bidentate BINAPs and monodentate phosphoramidites, and silylborane Me2 PhSi-Bpin accompanying sodium tert-butoxide in methanol was appropriate for the enantioselective hydrosilylation of the strained C=C double bond, and the resultant chiral difluorinated three-membered ring was unambiguously characterized. Subsequent activation of the silyl groups in enantio-enriched gem-difluorocyclopropanes showed substantial reduction of the enantiopurity, indicating cleavage of the distal C-C bond leading to the transient acyclic intermediates.
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