Direct Regio- and Diastereoselective Synthesis of δ-Lactams from Acrylamides and Unactivated Alkenes Initiated by RhIII-Catalyzed C-H Activation

被引:36
|
作者
Lee, Sumin [1 ]
Semakul, Natthawat [1 ]
Rovis, Tomislav [1 ]
机构
[1] Columbia Univ, Dept Chem, New York, NY 10027 USA
关键词
alkene functionalization; C-H activation; piperidines; Rhodium; delta-lactams; BOND; REACTIVITY; BENZAMIDES; ALKYNES; ACCESS;
D O I
10.1002/anie.201916332
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We report a Rh-III-catalyzed regio- and diastereoselective synthesis of delta-lactams from readily available acrylamide derivatives and unactivated alkenes. The reaction provides a rapid route to a diverse set of delta-lactams in good yield and stereoselectivity, which serve as useful building blocks for substituted piperidines. The regioselectivity of the reaction with unactivated terminal alkene is significantly improved by using Cp-t ligand on the Rh-III catalyst. The synthetic utility of the reaction is demonstrated by the preparation of a potential drug candidate containing a trisubstituted piperidine moiety. Mechanistic studies show that the reversibility of the C-H activation depends on the choice of Cp ligand on the Rh-III catalyst. The irreversible C-H activation is observed and becomes turnover-limiting with [(CpRhCl2)-Rh-t](2) as catalyst.
引用
收藏
页码:4965 / 4969
页数:5
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