The stereochemistry of 2,4- and 2,3-disubstituted-γ-butyrolactones

S. A M Tayyeb Hussain, W. David Ollis*, Christopher Smith, J. Fraser Stoddart

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

71 Scopus citations

Abstract

Relative configurational assignments have been made to the 2,4-dimethyl- (7), 2,4-di-t-butyl- (8), 2,4-diphenyl-(9), 4-methyl-2-phenyl- (10), and 2-methyl-3-phenyl- (31) γ-butyrolactones on the basis of the stereoselective synthesis of their cis-isomers, from the corresponding disubstituted but-2-en-4-olides (2)-(5) and 2-methylene-3-phenyl-γ- butyrolactone (41) by hydrogenation over palladium. The characteristic features from the 1H n.m.r. spectra of the cis- and trans-isomers of (7)-(10) have been employed to assign relative configurations to the 2-methyl-4-phenyl- (11), 2,4-diethyl- (12), 2-ethyl-4-methyl- (13), and 2-butyl-4-methyl- (14) γ-butyrolactones. Equilibration studies on seven 2,4-disubstituted γ-butyrolactones [(7)-(10) and (12)-(14)] indicate that (i) the free energy differences between cis- and trans-isomers are small, and (ii) the cis- is thermodynamically more stable than the trans-isomer in all cases. The opposite situation is true of the 2-methyl-3-phenyl-γ-butyro-lactones (31) where the trans-isomet is found to predominate at equilibrium. 1H N.m.r. spectroscopic data suggest that the conformational behaviour of the five-membered ring in 2,4-disubstituted γ-butyrolactones is different for diastereoisomers but is not influenced to any great extent by the nature of the substituent groupings.

Original languageEnglish (US)
Pages (from-to)1480-1492
Number of pages13
JournalJournal of the Chemical Society, Perkin Transactions 1
Issue number15
DOIs
StatePublished - 1975

ASJC Scopus subject areas

  • Chemistry(all)

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