Asymmetric Desymmetrization of 4,5-Epoxycyclohex-1-ene by Enantioselective Allylic Oxidation

作者：Tan Qitao; Hayashi Masahiko^*

来源：Organic Letters, 2009, 11(15): 3314-3317.

DOI：10.1021/ol901284v

Asymmetric desymmetrization of allylic oxidation of 4,5-epoxycyclohex-1-ene (1) took place in the presence of 2.5 mol % of Cu(CH(3)CN)(4)PF(6) and 3 mol % of chiral N,N-bidentate ligand (S)-2 to afford (3S,4S,5S)-3-benzoyfoxy-4,5-epoxycyclohex-1-ene (3) in 84% ee, which was increased up to > 99% ee after recrystallization of 3-4'-nitrobenzoyloxy derivative 6. Optically pure 6 proved to be a key intermediate for enantioselective synthesis of O-protected 2-deoxystreptamine (2-DOS) precursor 12.

• 出版日期2009-8-6