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We have developed a metal-free and highly diastereoselective ammonium-directed dihydroxylation of 3-aminocyclohex-1-enes upon treatment with Cl3CCO2H followed by mCPBA. The reaction mechanism involves protection of the amine by protonation, hydrogen-bonded delivery of the oxidant by the allylic ammonium ion formed in situ, followed by highly regioselective ringopening of the intermediate syn-epoxide by trichloroacetic acid, to give a 1,2-anti-2,3syn amino diol after deprotection. Meanwhile, oxidation of the corresponding tertiary amine N-oxide is entirely complementary and proceeds with high anti-diastereoselectivity to afford the corresponding 1,2-anti-2,3-anti amino diol after deprotection, consistent with the epoxidation reaction proceeding under steric or dipole control. The ammonium-directed oxidation protocol is general for a range of cyclic allylic and homoallylic amines and facilitates the metal-free synthesis of all four diastereoisomers of the corresponding 3-amino-1,2-diols, and has recently been employed as one of the key steps in the syntheses of (±)-1- deoxynojirimycin and (±)-1-deoxyaltronojirimycin.

Original publication

DOI

10.5059/yukigoseikyokaishi.68.1295

Type

Journal article

Journal

Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry

Publication Date

01/12/2010

Volume

68

Pages

1295 - 1306