TY - JOUR
T1 - Enantiospecific Syntheses of (+)-Crotepoxide, (+)-Boesenoxide, (+)-β-Senepoxide, (+)-Pipoxide Acetate, (-)-iso-Crotepoxide, (-)-Senepoxide, and (-)-Tingtanoxide from (-)-Quinic Acid
AU - Shing, Tony K.M.
AU - Tam, Eric K.W.
PY - 1998/3/6
Y1 - 1998/3/6
N2 - A convenient strategy that is ideally suited for the construction of all the naturally occurring cyclohexane diepoxides and cyclohexene epoxides is described. The key intermediate 12, a 1,3-cyclohexadiene, has been prepared from (-)-quinic acid in 11 steps with 18% overall yield. Singlet oxygen photooxygenation of the 1,3-cyclohexadiene followed by rearrangement of the resultant endoperoxides with either cobalt-meso-tetraphenylporphyrin or trimethyl phosphite afforded enantiopure (+)-crotepoxide, (+)-boesenoxide, and (-)-iso-crotepoxide or (-)-senepoxide, (+)-β-senepoxide, (+)-pipoxide acetate, and (-)-tingtanoxide, respectively.
AB - A convenient strategy that is ideally suited for the construction of all the naturally occurring cyclohexane diepoxides and cyclohexene epoxides is described. The key intermediate 12, a 1,3-cyclohexadiene, has been prepared from (-)-quinic acid in 11 steps with 18% overall yield. Singlet oxygen photooxygenation of the 1,3-cyclohexadiene followed by rearrangement of the resultant endoperoxides with either cobalt-meso-tetraphenylporphyrin or trimethyl phosphite afforded enantiopure (+)-crotepoxide, (+)-boesenoxide, and (-)-iso-crotepoxide or (-)-senepoxide, (+)-β-senepoxide, (+)-pipoxide acetate, and (-)-tingtanoxide, respectively.
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U2 - 10.1021/jo970907o
DO - 10.1021/jo970907o
M3 - Article
AN - SCOPUS:0032489474
SN - 0022-3263
VL - 63
SP - 1547
EP - 1554
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 5
ER -