Synthesis, structure and unusual reactivity of a stable 3-(oxazolidin-2-ylidene)thiophen-2-one
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Treatment of 2- and 3-thienyloxazolines with butyllithium and bis(trimethylsilyl) peroxide results in ring hydroxylation to give products which exist mainly as the oxazolidinylidenethiophenones. The 3-oxazolidinylidenethiophen-2-one is a rare example of a stable heterocyclic ortho-quinone methide analog which shows a varied pattern of reactivity, including both C- and O-alkylation, Michael addition via C-5 to an acetylenic ester, tetrachlorobenzannulation across positions 4 and 5, and formation of a hexacyclic fused-ring product with N-phenyltriazolinedione. Crystal structures of the products are dominated by inter- and intramolecular NH to CO hydrogen bonding.
Aitken , R A , Harper , A D & Slawin , A M Z 2016 , ' Synthesis, structure and unusual reactivity of a stable 3-(oxazolidin-2-ylidene)thiophen-2-one ' Journal of Organic Chemistry , vol 81 , no. 21 , pp. 10527-10531 . DOI: 10.1021/acs.joc.6b01309
Journal of Organic Chemistry
Copyright © 2016 American Chemical Society. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://dx.doi.org/10.1021/acs.joc.6b00628
The authors thank EPSRC (UK) for a DTA studentship (Grant EP/L505079/1) and the EPSRC UK National Mass Spectrometry Facility at Swansea University.
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