亲核试剂配位调控钯催化不对称烯丙基 C-H 烷基化反应的区域选择性。
Nucleophile Coordination Enabled Regioselectivity in Palladium-Catalyzed Asymmetric Allylic C-H Alkylation.
机构信息
Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China.
Center for Excellence in Molecular Synthesis of CAS, China.
出版信息
Angew Chem Int Ed Engl. 2019 Nov 18;58(47):16806-16810. doi: 10.1002/anie.201908960. Epub 2019 Oct 8.
Branched selectivity in asymmetric allylic C-H alkylation is enabled by using 2-acylimidazoles as nucleophiles in the presence of a chiral phosphoramidite-palladium catalyst. A wide range of terminal alkenes, including 1,4-dienes and allylarenes, are nicely tolerated and provide chiral 2-acylimidazoles in moderate to high yields and with high levels of regio-, and enantio-, and E/Z-selectivities. Mechanistic studies using density-functional theory calculations suggest a nucleophile-coordination-enabled inner-sphere attack mode for the enantioselective carbon-carbon bond-forming event.
手性膦酰胺-钯催化剂存在下，2-酰基咪唑作为亲核试剂，可实现不对称烯丙基 C-H 烷基化的支化选择性。各种末端烯烃，包括 1,4-二烯和烯丙基芳烃，都能很好地耐受，并以中等到高产率和高区域、对映和 E/Z 选择性提供手性 2-酰基咪唑。使用密度泛函理论计算的机理研究表明，手性碳-碳键形成反应的对映选择性为亲核配位启用的内球攻击模式。
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