Beilstein J. Org. Chem.2022,18, 1741–1748, doi:10.3762/bjoc.18.183
’-methoxy-γ-pyrone in one step. To construct the quaternary carbon of the 2,5-cyclohexadienone of the target, a strategy based on the Robinson-typeannulation of an aldehyde derived from α-crotyl-α’-methoxy-γ-pyrone was applied. The grafting of the simplified target’s side chain was demonstrated through an
oxidative anionic oxy-Cope rearrangement of the tertiary alcohol arising from the 1,2-addition of a 1,3-dimethylallyl reagent to 2,5-cyclohexadienone connected to the α’-methoxy-γ-pyrone motif.
Keywords: α’-methoxy-γ-pyrone; 2,5-cyclohexadienone; oxy-Cope; quaternary carbon; Robinson-typeannulation
to 2,5-cyclohexanedione 5 was accordingly updated and an approach to make use of the Robinson-typeannulation was devised from aldehyde 9, prepared by oxidation of α-crotyl-α’-methoxy-γ-pyrone 8 (Scheme 4). While its synthesis was initially investigated by the coupling of tri(n-butyl)crotylstannane
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Graphical Abstract
Scheme 1:
Routes to crispatene, photodeoxytridachione, aureothin, and tridachiapyrone B.