Formation of allenyl ketones, 3-ethynylcoumarins, and arylfurans, furylfurans, and furylthiophenes by flash vacuum thermolysis of 3-methylidenefuran-2(3 H)-ones

Koch, Rainer, Berstermann, Hans Michael and Wentrup, Curt (2014) Formation of allenyl ketones, 3-ethynylcoumarins, and arylfurans, furylfurans, and furylthiophenes by flash vacuum thermolysis of 3-methylidenefuran-2(3 H)-ones. Journal of Organic Chemistry, 79 1: 65-71. doi:10.1021/jo402139a


Author Koch, Rainer
Berstermann, Hans Michael
Wentrup, Curt
Title Formation of allenyl ketones, 3-ethynylcoumarins, and arylfurans, furylfurans, and furylthiophenes by flash vacuum thermolysis of 3-methylidenefuran-2(3 H)-ones
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
1520-6904
Publication date 2014-01-03
Year available 2013
Sub-type Article (original research)
DOI 10.1021/jo402139a
Volume 79
Issue 1
Start page 65
End page 71
Total pages 7
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Abstract Flash vacuum thermolysis (FVT) of 3-methylidenefuran-2(3H)-ones 3 causes cheletropic extrusion of CO with formation of allenyl ketones 4. o-Chloro- and o-bromophenylmethylidenefuranones also afford allenyl ketones upon flash vacuum thermolysis, but in addition, 3-ethynylcoumarins 6 are formed via E/Z isomerization of the methylidenefuranones, cyclization, halogen atom migration, and HCl (HBr) elimination. The presence of strongly electron-withdrawing groups (nitroaryl or acetyl) on the acylallene moiety causes rearrangement to give 2-arylfurans 10 and 13 as well as 2-furylfurans and 2-furylthiophenes 16 by cyclization of the allenyl ketones. The reaction mechanisms are supported by calculations at the M06-2X/6-311+G(d,p) level of theory.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes Published online: 12 December 2013.

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2014 Collection
School of Chemistry and Molecular Biosciences
 
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