Tetrahedron p. 5707 - 5738 (1996)
Update date:2022-07-29
Topics:
Pirrung, Michael C.
Nunn, David S.
We have studied the photochemistry of over 15 quinone cyclic monoketals, which were prepared by diol exchange from the dimethyl ketals, Swanton oxidation/hydrolysis, or direct ketalization. Their reactions in acidic media are generally explained by the classical mechanism for cyclohexadienone photochemical (di-π-methane) rearrangements: photocyclization to a cyclopropane-oxyallylcation that is protonated, followed by sovolysis. This reaction pathway provides, after hydrolysis, β-carboxy-substituted cyclopentenones. With a substituent at the β-position of the quinone monoketal, rearrangement selectivity is modestly in favor of the more substituted alkene product. With a substituent at the α-position of the quinone monoketal, rearrangement selectivity is strongly in favor of the less substituted alkene product. Possible mechanistic reasoning to explain these observations is offered.
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Doi:10.1016/j.cclet.2012.06.014
(2012)Doi:10.1021/om300542a
(2012)Doi:10.1246/cl.1991.2117
(1991)Doi:10.1021/om00044a039
(1992)Doi:10.1055/s-1991-28406
(1991)Doi:10.1002/chem.201706003
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