Silicon Acceleration of a
Tandem Alkene Isomerization/Electrocyclic
Ring-opening of 2‑Methyleneoxetanes to α,β-Unsaturated
Methylketones
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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 theory explains the
differential kinetics and stereoselectivities among substrates