Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - alpha-Acyloxynitroso dienophiles in [4+2] hetero Diels-Alder cycloadditions
T2 - mechanistic insights
AU - Calvet, Geraldine
AU - Coote, Susannah C.
AU - Blanchard, Nicolas
AU - Kouklovsky, Cyrille
PY - 2010/4/17
Y1 - 2010/4/17
N2 - alpha-Acyloxynitroso derivatives are a class of heterodienophiles leading to valuable 3,6-dihydro-1,2-oxazines or the corresponding aminoalcohols in good yields. The discovery that a beta-oxygenated moiety led to a domino [4+2] cycloaddition/sigma(N-O) bond cleavage in the presence of a catalytic amount of Lewis acid was investigated in detail, through kinetic profiling of the reaction both in the absence and presence of a promoter. These studies showed that the role of the Lewis acid was to accelerate the sigma(N-O) bond cleavage thereby promoting a highly reproducible sequence. In addition, our preliminary results on an asymmetric version of this domino sequence are reported. (C) 2010 Elsevier Ltd. All rights reserved.
AB - alpha-Acyloxynitroso derivatives are a class of heterodienophiles leading to valuable 3,6-dihydro-1,2-oxazines or the corresponding aminoalcohols in good yields. The discovery that a beta-oxygenated moiety led to a domino [4+2] cycloaddition/sigma(N-O) bond cleavage in the presence of a catalytic amount of Lewis acid was investigated in detail, through kinetic profiling of the reaction both in the absence and presence of a promoter. These studies showed that the role of the Lewis acid was to accelerate the sigma(N-O) bond cleavage thereby promoting a highly reproducible sequence. In addition, our preliminary results on an asymmetric version of this domino sequence are reported. (C) 2010 Elsevier Ltd. All rights reserved.
KW - ACYL-NITROSO COMPOUNDS
KW - LEAD TETRAACETATE OXIDATION
KW - N-O BOND
KW - ASYMMETRIC DIELS
KW - HYDROXAMIC ACID
KW - STEREOSELECTIVE CYCLOADDITIONS
KW - ACYLNITROSO DIENOPHILES
KW - CHLORONITROSO COMPOUNDS
KW - REDUCTIVE CLEAVAGE
KW - IMINIUM CATALYSIS
U2 - 10.1016/j.tet.2010.02.065
DO - 10.1016/j.tet.2010.02.065
M3 - Journal article
VL - 66
SP - 2969
EP - 2980
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 16
ER -