Silicon Acceleration of a Tandem Alkene Isomerization/Electrocyclic Ring-opening of 2-Methyleneoxetanes to α, β-Unsaturated Methylketones

E Farber, A Rudnitskaya, S Keshipeddy…

Index: Farber, Elisa; Rudnitskaya, Aleksandra; Keshipeddy, Santosh; Lao, Kendricks S.; Gascon, Jose A.; Howell, Amy R. Journal of Organic Chemistry, 2013 , vol. 78, # 22 p. 11213 - 11220

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Abstract

The first rearrangement of 2-methyleneoxetanes to α, β-unsaturated methylketones is reported. It is proposed that when these substrates are heated, the corresponding oxetenes are formed and subsequently undergo electrocyclic ring-opening to methyl vinylketones. In particular, α-silyl-α, β-unsaturated methylketones were isolated in moderate to high yields and with high stereoselectivities. Based on the proposed mechanism, density functional ...