Department of Chemistry, School of Arts and Sciences, The Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218-2685, USA.
Org Lett. 2011 Oct 7;13(19):5358-61. doi: 10.1021/ol202237j. Epub 2011 Sep 6.
Carboxylic acids were converted directly in 56-99% yields into methyl, n-butyl, and isopropyl ketones using excess cyanocuprates R(2)CuLi·LiCN. A substrate with a stereocenter α to the carboxylic acid was converted into ketones with very little loss of enantiomeric purity. A variety of functional groups were tolerated including aryl bromides. This direct transformation of a carboxylic acid into ketone with minimal tertiary alcohol formation is proposed to involve a relatively stable copper ketal tetrahedral intermediate.
羧酸在过量氰铜试剂 R(2)CuLi·LiCN 的作用下,以 56-99%的产率直接转化为甲基、正丁基和异丙基酮。具有羧酸α位立体中心的底物转化为酮时,对映体纯度损失很小。多种官能团包括芳基溴化物都能被容忍。这种羧酸到酮的直接转化,形成的叔醇很少,据推测涉及相对稳定的铜缩酮四面体中间体。