[3,3]-sigmatropic shifts and retro-ene rearrangements in cyanates, isocyanates, thiocyanates, and isothiocyanates of the form RX-YCN and RX-NCY

Koch, Rainer, Finnerty, Justin J., Murali, Sukumaran and Wentrup, Curt (2012) [3,3]-sigmatropic shifts and retro-ene rearrangements in cyanates, isocyanates, thiocyanates, and isothiocyanates of the form RX-YCN and RX-NCY. Journal of Organic Chemistry, 77 4: 1749-1759. doi:10.1021/jo2023069


Author Koch, Rainer
Finnerty, Justin J.
Murali, Sukumaran
Wentrup, Curt
Title [3,3]-sigmatropic shifts and retro-ene rearrangements in cyanates, isocyanates, thiocyanates, and isothiocyanates of the form RX-YCN and RX-NCY
Language of Title eng
Journal name Journal of Organic Chemistry   Check publisher's open access policy
Language of Journal Name eng
ISSN 0022-3263
1520-6904
Publication date 2012-02-17
Year available 2012
Sub-type Article (original research)
DOI 10.1021/jo2023069
Volume 77
Issue 4
Start page 1749
End page 1759
Total pages 11
Editor C. Dale Poulter
Place of publication Washington, DC, U.S.A.
Publisher American Chemical Society
Collection year 2013
Language eng
Formatted abstract
Retro-ene type [2π + 2π + 2σ] and [3,3]-sigmatropic shift reactions involving the substituent groups R in heteroatom-substituted cyanates and thiocyanates RX-YCN and the isomeric isocyanates and isothiocyanates of the type RX-NCY (X = CR2, NR′, O, or S; Y = O or S) have been investigated computationally at the B3LYP/6-311++G(d,p) level. Retro-ene reactions of alkyl derivatives of the title compounds afford alkenes, imines, carbonyl and thiocarbonyl compounds together with HNCO (HNCS) or HOCN (HSCN). [3,3]-Sigmatropic shifts (hetero-Cope rearrangements) of the corresponding allyl, propargyl, benzyl, and aryl derivatives causes allylic rearrangements, propargyl–allenyl rearrangement, conversion of benzyl cyanates to o-isocyanatotoluenes, and conversion of N-cyanatoarylamines to o-isocyanatoanilines, etc. The corresponding rearrangements of allyl thiocyanates, arylamino thiocyanates and isothiocyanates, and arylsulfenyl thiocyanates and isothiocyanates are also described.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2013 Collection
School of Chemistry and Molecular Biosciences
 
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Created: Tue, 06 Mar 2012, 08:47:58 EST by Lucy O'Brien on behalf of School of Chemistry & Molecular Biosciences