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Copper-catalyzed asymmetric dearomatizing amination of 2-naphthols: Csp2–N coupling via 1,3-reductive elimination

  • Aying Yihuo,
  • Maoping Pu,
  • Zheng Tan,
  • Jibang Liao,
  • Jiuqi Tan,
  • Qi-Lin Zhou,
  • Xiaohua Liu,
  • Xiaoming Feng

摘要

An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by N,N′-dioxide-copper(I) complex as a chiral catalyst was presented. A variety of optically active β-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained with high yield and enantioselectivity under mild reaction conditions. Mechanistic studies indicated that this Csp2–N dearomatizing coupling proceeds via 1,3-reductive elimination of phenolate-CuIII-amino intermediate in five-membered ring transition states. The origin of enantioselectivity has also been elucidated based on density functional theory calculations.