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Acylation of α-(N-carbamoyl)alkylcuprates and alkyl- or aryl(halo)cuprates
Authors:RKarl Dieter  Ram R SharmaHuayun Yu  Vinayak K Gore
Institution:Hunter Laboratory, Department of Chemistry, Clemson University, Clemson, SC 29634-0973, USA
Abstract:α-(N-Carbamoyl)alkylcuprates R2CuLi·LiX or RCuXLi (X=CN, Cl)] when prepared from THF soluble CuX·2LiCl (X=Cl, CN) undergo a reliable and generally high yield reaction with aroyl, alkanoyl, and alkenoyl chlorides to provide a rapid and efficient synthesis of α-carbamoyl ketones. Cuprates prepared from acyclic, cyclic, and a functionalized carbamate can be utilized. Although yields are a function of cuprate reagent and substrate structure, nearly quantitative yields can be obtained with reagents generated from 2RLi+CuCN·2LiCl. The use of reagents generated from CuCl·2LiCl are more efficient in the α-(N-carbamoyl)alkyl ligand, although yields are slightly lower. Acylation of alkyl(chloro)cuprates generated from one equivalent of CuCl·2LiCl and organolithium or Grignard reagents provides an efficient and high yield procedure for ketone synthesis.
Keywords:acylation  deprotonation  aryl cuprates  α-(N-carbamoyl)alkylcuprates
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