Matrix-IR Spectroscopic Investigations of the Thermolysis and Photolysis of Diazoamides

C Wentrup, H Bibas, A Kuhn, U Mitschke…

Index: Wentrup, Curt; Bibas, Herve; Kuhn, Arvid; Mitschke, Ullrich; McMills, Mark C. Journal of Organic Chemistry, 2013 , vol. 78, # 21 p. 10705 - 10717

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Citation Number: 7

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 ...