Primary and secondary α-halomethyl diazoketones generated via Arndt-Eistert chemistry with minimum loading of diazomethane efficiently alkylate aromatic amines in the presence of calcium oxide to furnish the corresponding α-arylamino diazoketones under full chemocontrol. Such a simple inorganic acid scavenger fully neutralizes the hydrohalic acid formed during the nucleophilic displacement which otherwise would immediately react to produce the corresponding α-haloketone. The methodology can be further exploited in analogous acylation-type processes on secondary arylamino diazoketones. In depth spectroscopic (1H, 13C, and 15N NMR) and crystallographic analyses document interesting structural features of these previously unknown diazo derivatives.
α-Arylamino Diazoketones: Diazomethane-Loading Controlled Synthesis, Spectroscopic Investigations, and Structural X-ray Analysis / Castoldi, L.; Ielo, L.; Holzer, W.; Giester, G.; Roller, A.; Pace, V.. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - 83:8(2018), pp. 4336-4347. [10.1021/acs.joc.7b03134]
α-Arylamino Diazoketones: Diazomethane-Loading Controlled Synthesis, Spectroscopic Investigations, and Structural X-ray Analysis
Pace V.
2018
Abstract
Primary and secondary α-halomethyl diazoketones generated via Arndt-Eistert chemistry with minimum loading of diazomethane efficiently alkylate aromatic amines in the presence of calcium oxide to furnish the corresponding α-arylamino diazoketones under full chemocontrol. Such a simple inorganic acid scavenger fully neutralizes the hydrohalic acid formed during the nucleophilic displacement which otherwise would immediately react to produce the corresponding α-haloketone. The methodology can be further exploited in analogous acylation-type processes on secondary arylamino diazoketones. In depth spectroscopic (1H, 13C, and 15N NMR) and crystallographic analyses document interesting structural features of these previously unknown diazo derivatives.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
