Base and catalyst-free synthesis of nitrobenzodiazepines via a cascade N-nitroallylation-intramolecular aza-Michael addition involving o-phenylenediamines and nitroallylic acetates

Nair, Divya K. ; Sivanandan, Sudheesh T. ; Kendrekar, Pravin ; Namboothiri, Irishi N.N. (2019) Base and catalyst-free synthesis of nitrobenzodiazepines via a cascade N-nitroallylation-intramolecular aza-Michael addition involving o-phenylenediamines and nitroallylic acetates Tetrahedron, 75 (51). p. 130761. ISSN 0040-4020

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Official URL: http://doi.org/10.1016/j.tet.2019.130761

Related URL: http://dx.doi.org/10.1016/j.tet.2019.130761

Abstract

A [4+3] annulation of o-phenylenediamines with primary nitroallylic acetates affords nitrobenzodiazepines (NBDZs) in good to excellent yield. The reaction which proceeds in MeOH at room temperature in the absence of any base or catalyst involves a cascade SN2 N-nitroallylation-intramolecular aza-Michael addition sequence. In the case of mono-N-arylated o-phenylenediamines and o-aminobenzamides, the reaction stops at the SN2 stage affording nitroallylic amines. On the other hand, reaction of o-aminobenzamides with secondary nitroallylic acetates delivers SN2′ products. Formation of stable SN2 and SN2′ products provides insights into the reactivity of primary and secondary nitroallylic acetates and also the mechanism of formation of nitrobenzodiazepines.

Item Type:Article
Source:Copyright of this article belongs to Elsevier Science.
ID Code:121315
Deposited On:14 Jul 2021 09:18
Last Modified:14 Jul 2021 09:18

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