31366-13-9Relevant academic research and scientific papers
Matrix-IR spectroscopic investigations of the thermolysis and photolysis of diazoamides
Wentrup, Curt,Bibas, Herve,Kuhn, Arvid,Mitschke, Ullrich,McMills, Mark C.
, p. 10705 - 10717 (2013/11/19)
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 di
Ultrafast time-resolved infrared spectroscopy study of the photochemistry of N,N-diethyldiazoacetamide: rearrangement in the excited state
Zhang, Yunlong,Burdzinski, Gotard,Kubicki, Jacek,Platz, Matthew S.
supporting information; body text, p. 9646 - 9647 (2011/03/20)
(Graph Presented) Ultrafast infrared spectroscopy shows that in chloroform, β-lactam is formed immediately after the laser pulse but γ-lactam is formed from both slow and fast processes. It is concluded that β-lactam is formed from the diazoamide excited state via the rearrangement in the excited state (RIES) mechanism and that γ-lactam is formed from both RIES and carbene. In methanol, both carbene decay and the rise of amide ether product are observed directly. Predictions from density functional theory calculations are consistent with these observations.
Rediscovering copper-based catalysts for intramolecular carbon-hydrogen bond functionalization by carbene insertion
Martin, Carmen,Belderrain, Tomas R.,Perez, Pedro J.
supporting information; scheme or table, p. 4777 - 4781 (2009/12/08)
A series of TpxCu complexes (Tpx = hydrotrispyrazolylborate ligand) have been tested as catalysts for the decomposition of several diazoacetates and N,N-disubstituted diazoacetamides and the subsequent formation of lactones and lacta
Substituent Effects on the Product Distribution in Diazo Amide Photochemistry. Role of Ground-State Conformational Populations
Tomioka, Hideo,Kondo, Masato,Izawa, Yasuji
, p. 1090 - 1094 (2007/10/02)
Effects of substituents on the photochemical processes of several α-diazo amides (1a-f) have been studied .Irradiation of 1b in ethyl ether and acetone afforded, in addition to a β-lactam, the reaction products with the solvents, ie., EtOCH2CONMe2 and 1,3-dioxolane, respectively, whereas similar irradiation of 1a in these solvents gave only intramolecular reaction products, ie., β- and γ-lactams.Displacement of oneof the alkyl groups on the amide nitrogen with a Ph group markedly changed its photochemical processes.Thus irradiations of 1c and 1d in MeOH gave oxindole almost exclusively.Introduction of an acetyl group on the diazo carbon also caused a change in the product distributions.Photolysis of 1e in methanol gave, for exaple, the Wolff rearrangement (WR) product of Me migration and a β-lactam, whereas similar irradiation of 1f afforded WR product and oxindole.The results are interpreted as indicating that the β-lactam, the oxindole, and the WR product are derived from the excited singlet state of s-Z form of the diazo amide itself, whereas that of s-E form dissociates nitrogen to generate singlet carbene, and that populations of each conformers in the ground state are important in determining the photochemical processes of the α-diazo amide.
