Novel Fragmentation Reaction of 2-Alkyl- and 2,4-Dialkyl-3-iodo-1-oxocyclohexan-2,4-carbolactones
- 1 October 2004
- journal article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 69 (22), 7728-7733
- https://doi.org/10.1021/jo0490853
Abstract
2-Alkyl- and 2,4-dialkyl-3-iodo-1-oxocyclohexan-2,4-carbolactones undergo lithium hydroxide- and lithium alkoxide-induced fragmentation reactions to provide butenolides, γ-hydroxycyclohexenones, and/or γ-butyrolactones. In general, product distribution is governed by two factors: (1) the nature of nucleophiles and (2) the steric bulkiness of the substituents at C-2 and C-4 of the cyclohexanones. Lithium hydroxide-induced fragmentation provides butenolides and γ-hydroxycyclohexenones. In contrast, lithium alkoxide-promoted fragmentation results in predominantly 5-substituted γ-butyrolactones along with a small amount of butenolides in limited cases. Fragmentation products induced by lithium hydroxide are largely influenced by the steric bulkiness of the substituents at C-2 and C-4 of the cyclohexanone ring. The bulky substituents render the exclusive formation of butenolides.Keywords
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