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Synthesis 2018; 50(03): 617-624
DOI: 10.1055/s-0036-1590943
paper
© Georg Thieme Verlag Stuttgart · New York

Oxidative Functionalization of Cyclic N-Arylamines with Nitromethane and TMSCN Using the T-HYDRO/t-BuOK System

Gunda Ananda Rao
School of Chemistry, University of Hyderabad, Central University P.O, Hyderabad-500046, India   Email: mpsc@uohyd.ac.in
,
Mariappan Periasamy*
School of Chemistry, University of Hyderabad, Central University P.O, Hyderabad-500046, India   Email: mpsc@uohyd.ac.in
› Author AffiliationsWe are thankful to the SERB-DST, New Delhi for support (SB/S5/GC-01/2014) to M.P. and for the DST support to the School of Chemistry under the FIST and IRPHA programs. Support from CSIR-HRDG (No: 02/0176/14/EMR-II) to M.P. and from the UGC under the UPE and CAS programs is also gratefully acknowledged. G.A.R. is grateful to the UGC (New Delhi) for a fellowship.
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Publication History

Received: 26 August 2017

Accepted after revision: 05 October 2017

Publication Date:
06 November 2017 (online)

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Abstract

Tertiary cyclic N-arylamines react with nitromethane in the presence of the tert-butyl hydroperoxide (T-HYDRO)/t-BuOK system to give β-nitroamines in up to 90% yield. When TMSCN is used in place of nitromethane, α-aminonitriles are obtained in up to 96% yield. The method is suitable for several unactivated cyclic arylamine substrates. These transformations are rationalized considering the formation of the corresponding iminium ion intermediates via an initial electron transfer process.

Key words

N-arylamines - iminium ions - enamines - α-aminonitriles - β-nitroamines

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    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590943.
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