Nucleophile Coordination Enabled Regioselectivity in Palladium-Catalyzed Asymmetric Allylic C-H Alkylation

被引:41
作者
Fan, Lian-Feng [1 ,2 ]
Luo, Shi-Wei [1 ,2 ]
Chen, Shu-Sen [1 ,2 ]
Wang, Tian-Ci [1 ,2 ]
Wang, Pu-Sheng [1 ,2 ]
Gong, Liu-Zhu [1 ,2 ,3 ]
机构
[1] Univ Sci & Technol China, Hefei Natl Lab Phys Sci Microscale, Hefei 230026, Anhui, Peoples R China
[2] Univ Sci & Technol China, Dept Chem, Hefei 230026, Anhui, Peoples R China
[3] Chinese Acad Sci, Ctr Excellence Mol Synth, Beijing, Peoples R China
关键词
allylic compounds; chirality; palladium; reaction mechanisms; synthetic methods; TERMINAL OLEFINS; 2-ACYL IMIDAZOLES; ALLYLATION; FUNCTIONALIZATION; STRATEGY; COMPLEX; AMINATION; OXIDATION; LIGANDS; BONDS;
D O I
10.1002/anie.201908960
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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.
引用
收藏
页码:16806 / 16810
页数:5
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