Ammonium-directed oxidation of cyclic allylic and homoallylic amines

Christopher W. Bond; Alexander J. Cresswell; Stephen G. Davies; Ai M. Fletcher; Wataru Kurosawa; James A. Lee; Paul M. Roberts; Angela J. Russell; Andrew D. Smith; James E. Thomson

doi:10.1021/jo9012783

Ammonium-directed oxidation of cyclic allylic and homoallylic amines

Christopher W. Bond, Alexander J. Cresswell, Stephen G. Davies, Ai M. Fletcher, Wataru Kurosawa, James A. Lee, Paul M. Roberts, Angela J. Russell, Andrew D. Smith, James E. Thomson

University of Oxford

Research output: Contribution to journal › Article › peer-review

62 Citations (SciVal)

Abstract

(Chemical Equation Presented) The ammonium-directed olefinic oxidation of a range of cyclic allylic and homoallylic amines has been investigated. Functionalization of a range of allylic 3-(N,N-dibenzylamino)cycloalk-1-enes with m-CPBA in the presence of Cl3CCO2H gives exclusively the corresponding syn-epoxide for the 5-membered ring (>99:1 dr), the anti-epoxide for the 8-membered ring (>99:1 dr), and predominantly the anti-epoxide for the 7-membered ring (94:6 dr). Oxidation of the homoallylic amines 3-(Nbenzylamino) methylcyclohex-1-ene and 3-(N,N-dibenzylamino)methylcyclohex-1-ene gave, in both cases, the correspondingN-protected 1,2-anti-2,3-syn-3-aminomethylcyclohexane- 1,2-diol with high levels of diastereoselectivity (g90:10 dr). The versatile synthetic intermediates resulting from these oxidation reactions are readily transformed into a range of amino diols.

Original language	English
Pages (from-to)	6735-6748
Number of pages	14
Journal	Journal of Organic Chemistry
Volume	74
Issue number	17
DOIs	https://doi.org/10.1021/jo9012783
Publication status	Published - 4 Sept 2009

ASJC Scopus subject areas

Organic Chemistry

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10.1021/jo9012783

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title = "Ammonium-directed oxidation of cyclic allylic and homoallylic amines",

abstract = "(Chemical Equation Presented) The ammonium-directed olefinic oxidation of a range of cyclic allylic and homoallylic amines has been investigated. Functionalization of a range of allylic 3-(N,N-dibenzylamino)cycloalk-1-enes with m-CPBA in the presence of Cl3CCO2H gives exclusively the corresponding syn-epoxide for the 5-membered ring (>99:1 dr), the anti-epoxide for the 8-membered ring (>99:1 dr), and predominantly the anti-epoxide for the 7-membered ring (94:6 dr). Oxidation of the homoallylic amines 3-(Nbenzylamino) methylcyclohex-1-ene and 3-(N,N-dibenzylamino)methylcyclohex-1-ene gave, in both cases, the correspondingN-protected 1,2-anti-2,3-syn-3-aminomethylcyclohexane- 1,2-diol with high levels of diastereoselectivity (g90:10 dr). The versatile synthetic intermediates resulting from these oxidation reactions are readily transformed into a range of amino diols.",

author = "Bond, {Christopher W.} and Cresswell, {Alexander J.} and Davies, {Stephen G.} and Fletcher, {Ai M.} and Wataru Kurosawa and Lee, {James A.} and Roberts, {Paul M.} and Russell, {Angela J.} and Smith, {Andrew D.} and Thomson, {James E.}",

year = "2009",

month = sep,

day = "4",

doi = "10.1021/jo9012783",

language = "English",

volume = "74",

pages = "6735--6748",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

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T1 - Ammonium-directed oxidation of cyclic allylic and homoallylic amines

AU - Bond, Christopher W.

AU - Cresswell, Alexander J.

AU - Davies, Stephen G.

AU - Fletcher, Ai M.

AU - Kurosawa, Wataru

AU - Lee, James A.

AU - Roberts, Paul M.

AU - Russell, Angela J.

AU - Smith, Andrew D.

AU - Thomson, James E.

PY - 2009/9/4

Y1 - 2009/9/4

N2 - (Chemical Equation Presented) The ammonium-directed olefinic oxidation of a range of cyclic allylic and homoallylic amines has been investigated. Functionalization of a range of allylic 3-(N,N-dibenzylamino)cycloalk-1-enes with m-CPBA in the presence of Cl3CCO2H gives exclusively the corresponding syn-epoxide for the 5-membered ring (>99:1 dr), the anti-epoxide for the 8-membered ring (>99:1 dr), and predominantly the anti-epoxide for the 7-membered ring (94:6 dr). Oxidation of the homoallylic amines 3-(Nbenzylamino) methylcyclohex-1-ene and 3-(N,N-dibenzylamino)methylcyclohex-1-ene gave, in both cases, the correspondingN-protected 1,2-anti-2,3-syn-3-aminomethylcyclohexane- 1,2-diol with high levels of diastereoselectivity (g90:10 dr). The versatile synthetic intermediates resulting from these oxidation reactions are readily transformed into a range of amino diols.

AB - (Chemical Equation Presented) The ammonium-directed olefinic oxidation of a range of cyclic allylic and homoallylic amines has been investigated. Functionalization of a range of allylic 3-(N,N-dibenzylamino)cycloalk-1-enes with m-CPBA in the presence of Cl3CCO2H gives exclusively the corresponding syn-epoxide for the 5-membered ring (>99:1 dr), the anti-epoxide for the 8-membered ring (>99:1 dr), and predominantly the anti-epoxide for the 7-membered ring (94:6 dr). Oxidation of the homoallylic amines 3-(Nbenzylamino) methylcyclohex-1-ene and 3-(N,N-dibenzylamino)methylcyclohex-1-ene gave, in both cases, the correspondingN-protected 1,2-anti-2,3-syn-3-aminomethylcyclohexane- 1,2-diol with high levels of diastereoselectivity (g90:10 dr). The versatile synthetic intermediates resulting from these oxidation reactions are readily transformed into a range of amino diols.

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Ammonium-directed oxidation of cyclic allylic and homoallylic amines

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