Continuous flow synthesis of ketones from carbon dioxide and organolithium or grignard reagents
We describe an efficient continuous flow synthesis of ketones from CO 2 and organolithium or Grignard reagents that exhibits significant advantages over conventional batch conditions in suppressing undesired symmetric ketone and tertiary alcohol byproducts. We observed an unprecedented solvent-dependence of the organolithium reactivity, the key factor in governing selectivity during the flow process. A facile, telescoped three-step-one-flow process for the preparation of ketones in a modular fashion through the in-line generation of organometallic reagents is also established.
Wu, Jie,Yang, Xiaoqing,He, Zhi,Mao, Xianwen,Hatton, T. Alan,Jamison, Timothy F.
supporting information
p. 8416 - 8420
(2014/08/18)
Salt effects on the reactivity and the stability of organomanganese reagents
The reactivity and the stability of organomanganese reagents prepared from the ate complexes MnX2·2LiBr (X= Br,I) and MnCl2·R4NX (X= Br, Cl) were studied. The preparation and the use for synthetic applications of stable sec- and tert-alkylmanganese bromides in ether as well as the acylation of RMnCl by R'COOCOOEt in THF were successfully achieved for the first time.