Matrix-IR spectroscopic investigations of the thermolysis and photolysis of diazoamides

Wentrup, Curt, Bibas, Herve, Kuhn, Arvid, Mitschke, Ullrich and McMills, Mark C. (2013) Matrix-IR spectroscopic investigations of the thermolysis and photolysis of diazoamides. Journal of Organic Chemistry, 78 21: 10705-10717. doi:10.1021/jo401695x


Author Wentrup, Curt
Bibas, Herve
Kuhn, Arvid
Mitschke, Ullrich
McMills, Mark C.
Title Matrix-IR spectroscopic investigations of the thermolysis and photolysis of diazoamides
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
1520-6904
Publication date 2013-11-01
Sub-type Article (original research)
DOI 10.1021/jo401695x
Volume 78
Issue 21
Start page 10705
End page 10717
Total pages 13
Place of publication Washington, DC, United States
Publisher American Chemical Society
Collection year 2014
Language eng
Subject 1605 Policy and Administration
Abstract Matrix photolysis of N,N-dialkyldiazoacetamides 1a-d at 7-10 K results in either the formation of C-H insertion products (in case of N,N-dimethyl and N,N-diethyl diazoamides) or almost exclusive Wolff rearrangement to ketenes (in the case of the cyclic diazoamides N-(diazoacetyl)azetidine and N-(diazoacetyl)pyrrolidine). This can be ascribed to higher activation barriers for the approach of the singlet carbene p orbital in 5 (or of the diazo carbon in an excited state of 1) to the stronger and "tied back" nature of the C-H bonds in the cyclic substituents. In contrast, flash vacuum thermolysis (FVT) of diazoamides 1a-d, in which reactions of excited states are excluded, gives rise to clean C-H insertion with only minor Wolff rearrangement to ketenes.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

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