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Synthesis of (±) Wine Lactone and Its Analogues by a Diels–Alder Approach
Author(s) -
O'Connor Patrick D.,
Kim U Bin,
Brimble Margaret A.
Publication year - 2009
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200900486
Subject(s) - chemistry , intramolecular force , lactone , cycloaddition , diastereomer , stereochemistry , ether , aldol reaction , diels–alder reaction , silyl ether , organic chemistry , silylation , catalysis
A novel route to (±)‐wine lactone ( 1 ) by a cis ‐selective kinetically controlled intramolecular Diels–Alder (IMDA) cycloaddition of the linear triene 2 is reported. The triene precursor was synthesised by TBAF‐catalysed coupling of an acyl fluoride with an silyl enol ether. Four butadienyl but‐3‐enoates were prepared and cyclised under mild conditions to give a series of wine lactone analogues. The diastereoselectivity of the IMDA cycloadditions was determined by NMR spectroscopy and GC‐MS, whereby the formation of the natural cis ‐configured wine lactone ( 1 ) was established. The diastereomeric IMDA transition states were optimised by using density functional theory at the B3LYP/6‐31+G(d) level, and the Boltzmann populations of the electronic energies were found to correlate well with the experimentally observed diastereoselectivity.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)