Direct Enantioselective α-Allylation of Unfunctionalized Cyclic Ketones with Alkynes through Pd-Amine Cooperative Catalysis
Direct Enantioselective α-Allylation of Unfunctionalized Cyclic Ketones with Alkynes through Pd-Amine Cooperative Catalysis
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DOI：
10.1002/chem.201802273
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发表时间：
2018-07-05
影响因子：
4.3
通讯作者：
Zhao, Yu
中科院分区：
文献类型：
--
作者：
Lee, Jin Tu Danence;Zhao, Yu
首次报道了以炔为试剂的非官能化环酮的直接不对称选择性α-烯丙基化反应。该转化使用简单的程序，使用市售钯、手性双膦配体和手性胺催化剂，并以良好至高的对映体纯度提供具有α-叔立构中心的有价值的酮。在该转化中，含有（S）-DI-FLUORPHOS配体的手性钯络合物催化炔异构化为亲电烯丙基钯物质，其被（R）-脯氨醇与酮底物缩合原位生成的烯胺攻击。
The first direct enantioselective alpha-allylation of unfunctionalized cyclic ketones using alkynes as an economical choice of reagent is reported. This transformation uses a simple procedure with commercially available palladium, chiral bisphosphine ligand and chiral amine catalysts, and affords valuable ketones with a alpha-tertiary stereocenter in good to high enantiopurity. In this transformation, a chiral palladium complex containing the (S)-DI-FLUORPHOS ligand catalyzes the isomerization of alkynes into an electrophilic allylpalladium species, which is attacked by the enamine generated in situ from the condensation of (R)-prolinol with the ketone substrate.