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First total syntheses of the phytotoxins solanapyrones D and E via the domino Michael protocol
Hisahiro Hagiwara1, Katsuhiro Kobayashi, Shigeki Miya
1Graduate School of Science and Technology, Niigata University, 8050, 2-nocho, Ikarashi, Niigata 950-2181, Japan. hagiwara@gs.nigata-u.ac.jp
Abstract:
The phytotoxins solanapyrones D (1) and E (2) have been synthesized from the decalone prepared by the domino Michael reaction of the kinetic enolate of optically pure acetylcyclohexene with methyl crotonate. The decalone was transformed into a solanapyrone core by equilibration into thermodynamically stable trans-decalone (11), dehydroxylation, and dehydration. Condensation of a methyl acetoacetate equivalent followed by cyclization installed a pyrone moiety. Introduction of a formyl or hydroxymethyl unit into the pyrone ring via Pummerer related reactions furnished solanapyrones D (1) and E (2).
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