[2+2] Photocycloaddition Studies on Complex Tetronic Acid Esters Related to the Synthesis of Cembranoid Diterpenes

Abstract

Twelve different tetronic acid esters bearing two potentially reactive olefinic groups were prepared and subjected to [2+2] photocycloaddition reactions by irradiation at λ = 254 nm in tert-butanol (5 mM). The diastereoselectivity and regioselectivity of the reaction was studied with regard to the synthesis of cembranoid diterpenes. When the tetronic acid core carried an alk-3-enyl substituent in the γ-position and an alk-3-enyloxy substituent in the β-position, the undesired γ-products prevailed and were formed in 48–81% yield. Altering the γ-alk-3-enyl substituent into an alk-3-ynyl or alk-2-ynyl substituent, resulted in formation of the desired β-photocycloaddition products. The latter products were obtained in yields of 56–88%, with two out of three products exhibiting very high regio- and diastereoselectivity.

Key words

[2+2] cycloadditions - cyclobutanes - regioselectivity - heterocycles - photochemistry

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