De Mayo Photocycloaddition and Construction of Basic Framework for Spiro- and Bridged-sesquiterpenes

Abstract

The photocyclo-adducts, the opening products and radical recombination products 3～10 were obtained by de Mayo reaction of 3-isopropylidene-6-methylcyclohexene with methyl 2,4-dioxopentanoate. The photocyclo-adduct 3 was subjected to retro-aldol rearrangement to yield the substituted-cyclohexene 4. In acid or basic condition the recyclization of the opening product was carried out, and spirocyclic and bridged compounds 11～14 were obtained by intramolecular Claisen condensation. The reaction mechanisms were discussed and the structures of all compounds were assigned based on the data derived from IR, ¹H NMR ¹³C CMR and elemental analysis.

Key words: spirocyclic compound, bridged compound, Claisen condensation, photocycloaddition

Cite this article

WANG Jin-Jun*^,1,JI Jian-Ye²,MORI Akira³. De Mayo Photocycloaddition and Construction of Basic Framework for Spiro- and Bridged-sesquiterpenes[J]. Chin. J. Org. Chem., 2006, 26(05): 653-659.

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De Mayo光环加成和桥(螺)环倍半萜基本碳架的构建