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Chemistry (Weinheim an der Bergstrasse, Germany)

Studies on thermal reactivity of beta-(1,2-allenyl)butenolides and 2-allyl-3-allenylcyclohex-2-enones.


PMID 18213559

Abstract

A series of thermal pericyclic reactions of beta-allenylfuranones have been studied. It was observed that beta-allenylfuranones would undergo 1,5-hydrogen shift to afford a new type of trienes upon heating. Due to their high reactivity, these trienes would undergo subsequent pericyclic reactions based on the nature of the substituent group R: When R is an alkyl group, the intermediate 4a or 4b would undergo a further 1,7-hydrogen shift to afford a more stable conjugated triene 3; with R being phenyl or cyclopropyl group, the 1,7-hydrogen shift was inhibited and the 4-type conjugated triene would form a six-membered ring 5 via 6 pi-electrocyclization. Interestingly, introducing another C=C double bond into the triene intermediate (R = CH=CH2, the 18-type intermediate would undergo 8 pi-electrocyclization reaction to form an eight-membered ring. Such a transformation was also observed with 2-allyl-3-allenylcyclohex-2-enones. The deuterium-labeling mechanistic studies show that the alkyl groups at the allenyl moiety of 1 participated in the isomerization process via 1,7-hydrogen shifts between 18 A, 20 A, and 29 A.

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