通过硅辅助的C-F键活化，经由MBH氟化物的对映选择性乙氧羰基二氟甲基化反应合成手性二氟亚甲基化合物。
Synthesis of Chiral -Difluoromethylene Compounds by Enantioselective Ethoxycarbonyldifluoromethylation of MBH Fluorides via Silicon-Assisted C-F Bond Activation.
作者信息
Sumii Yuji, Nagasaka Takato, Wang Jiandong, Uno Hiroto, Shibata Norio
机构信息
Department of Life Science and Applied Chemistry, Department of Nanopharmaceutical Sciences, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-5888, Japan.
Institute of Advanced Fluorine-Containing Materials, Zhejiang Normal University, 688 Yingbin Avenue, 321004 Jinhua, China.
出版信息
J Org Chem. 2020 Dec 4;85(23):15699-15707. doi: 10.1021/acs.joc.0c02201. Epub 2020 Nov 4.
The enantioselective ethoxycarbonyldifluoromethylation of Morita-Baylis-Hillman (MBH) fluorides with MeSiCFCOEt under organocatalysis is described. Moderately functionalized chiral -difluoromethylene compounds with a stereogenic "C-CF-C*" unit were synthesized in high yields with high enantioselectivities. The initial C-F bond activation is assisted by the silicon atom via a dual S2'-S2' stepwise pathway. Dynamic kinetic resolution of the MBH-fluorides explained the high yields and high ee's of the products. The method was extended to the enantioselective introduction of "Het-CF" units.
描述了在有机催化下，用MeSiCFCOEt对森田-贝利斯-希尔曼（MBH）氟化物进行对映选择性乙氧基羰基二氟甲基化反应。合成了具有立体异构“C-CF-C*”单元的中等官能化手性二氟亚甲基化合物，产率高且对映选择性高。初始的C-F键活化通过硅原子经由双S2'-S2'逐步途径得到辅助。MBH氟化物的动态动力学拆分解释了产物的高产率和高对映体过量值。该方法扩展到了“Het-CF”单元的对映选择性引入。
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