Synthesis, structure and unusual reactivity of a stable 3-(oxazolidin-2-ylidene)thiophen-2-one

R Alan Aitken; Andrew David Harper; Alexandra Martha Zoya Slawin

doi:10.1021/acs.joc.6b01309

Synthesis, structure and unusual reactivity of a stable 3-(oxazolidin-2-ylidene)thiophen-2-one

R Alan Aitken, Andrew David Harper, Alexandra Martha Zoya Slawin

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Abstract

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.

Original language	English
Pages (from-to)	10527-10531
Number of pages	5
Journal	The Journal of Organic Chemistry
Volume	81
Issue number	21
Early online date	15 Jul 2016
DOIs	https://doi.org/10.1021/acs.joc.6b01309
Publication status	Published - 4 Nov 2016

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10.1021/acs.joc.6b01309

Aitken_2016_JOC_UnusualReactivity_AM
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
Accepted author manuscript, 303 KB

R Alan Aitken
- raast-andrews.acuk
- School of Chemistry - Professor
- EaSTCHEM
Person: Academic

Synthesis, structure and unusual reactivity of a stable 3-(oxazolidin-2-ylidene)thiophen-2-one (dataset)
Aitken, R. A. (Creator), Harper, A. D. (Creator) & Slawin, A. M. Z. (Creator), Cambridge Crystallographic Data Centre, 2016
https://dx.doi.org/10.5517/ccdc.csd.cc1lr2p3 and 3 more links, https://dx.doi.org/10.5517/ccdc.csd.cc1lr2q4, https://dx.doi.org/10.5517/ccdc.csd.cc1lr2r5, https://dx.doi.org/10.5517/ccdc.csd.cc1lr2s6 (show fewer)
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title = "Synthesis, structure and unusual reactivity of a stable 3-(oxazolidin-2-ylidene)thiophen-2-one",

abstract = "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.",

author = "Aitken, {R Alan} and Harper, {Andrew David} and Slawin, {Alexandra Martha Zoya}",

note = "The authors thank EPSRC (UK) for a DTA studentship (Grant EP/L505079/1) and the EPSRC UK National Mass Spectrometry Facility at Swansea University.",

year = "2016",

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day = "4",

doi = "10.1021/acs.joc.6b01309",

language = "English",

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pages = "10527--10531",

journal = "The Journal of Organic Chemistry",

issn = "0022-3263",

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T1 - Synthesis, structure and unusual reactivity of a stable 3-(oxazolidin-2-ylidene)thiophen-2-one

AU - Aitken, R Alan

AU - Harper, Andrew David

AU - Slawin, Alexandra Martha Zoya

N1 - The authors thank EPSRC (UK) for a DTA studentship (Grant EP/L505079/1) and the EPSRC UK National Mass Spectrometry Facility at Swansea University.

PY - 2016/11/4

Y1 - 2016/11/4

N2 - 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.

AB - 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.

U2 - 10.1021/acs.joc.6b01309

DO - 10.1021/acs.joc.6b01309

M3 - Article

SN - 0022-3263

VL - 81

SP - 10527

EP - 10531

JO - The Journal of Organic Chemistry

JF - The Journal of Organic Chemistry

IS - 21

ER -

Synthesis, structure and unusual reactivity of a stable 3-(oxazolidin-2-ylidene)thiophen-2-one

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Synthesis, structure and unusual reactivity of a stable 3-(oxazolidin-2-ylidene)thiophen-2-one (dataset)

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