Copper‐Catalyzed Aqueous N−O Bond Cleavage of 2‐Oxa‐3‐Azabicyclo Compounds to Cyclic cis‐1,4‐Amino Alcohols

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Abstract
The N−O bond cleavage of 2‐oxa‐3‐azabicyclo substrates, which are readily prepared by the hetero Diels‐Alder reaction between nitroso dienophiles and cyclic 1,3‐dienes, was effectively catalyzed by heterogeneous copper‐on‐carbon (Cu/C) under aqueous conditions to give the corresponding cyclic cis‐1,4‐amino alcohol derivatives. The present method was applied to the direct incorporation of the hydroxy and amino groups derived from a nitroso substrate into cyclic 1,3‐dienes with cis‐selectivity by the combination of the in situ formation of 2‐oxa‐3‐azabicyclo compounds and following Cu/C‐catalyzed N−O bond cleavage. The obtained cis‐4‐aminocyclohexenols, derived from cyclohexadiene as a cyclic 1,3‐diene, could be selectively oxidized by using the ruthenium‐on‐carbon (Ru/C) catalyst under oxygen atmosphere to the corresponding 4‐aminocyclohexenones at 50–65 °C or para‐iminoquinones at 100–110 °C as useful reactive synthetic precursors.
Funding Information
  • Japan Society for the Promotion of Science (18J14010)
  • Takeda Science Foundation

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