TY - JOUR
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.
UR - http://www.scopus.com/inward/record.url?scp=69549117003&partnerID=8YFLogxK
UR - https://doi.org/10.1021/jo9012783
U2 - 10.1021/jo9012783
DO - 10.1021/jo9012783
M3 - Article
AN - SCOPUS:69549117003
SN - 0022-3263
VL - 74
SP - 6735
EP - 6748
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 17
ER -