alpha-Acyloxynitroso dienophiles in [4+2] hetero Diels-Alder cycloadditions: mechanistic insights

作者：Calvet Geraldine; Coote Susannah C; Blanchard Nicolas^*; Kouklovsky Cyrille

来源：Tetrahedron, 2010, 66(16): 2969-2980.

DOI：10.1016/j.tet.2010.02.065

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.

• 出版日期2010-4-17