Synthesis 2013; 45(13): 1719-1729
DOI: 10.1055/s-0033-1338867
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© Georg Thieme Verlag Stuttgart · New York

Regiospecific Synthesis of Novel Cyclic Nitrostyrenes and 3-Substituted 2-Nitronaphthalenes

Craig Keene
Division of Chemistry, Department of Biochemistry, UT Southwestern Medical Center, 5323 Harry Hines Blvd, Dallas TX 75390, USA   Fax: +1(214)6488856   Email: laszlo.kurti@utsouthwestern.edu
,
László Kürti*
Division of Chemistry, Department of Biochemistry, UT Southwestern Medical Center, 5323 Harry Hines Blvd, Dallas TX 75390, USA   Fax: +1(214)6488856   Email: laszlo.kurti@utsouthwestern.edu
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Publication History

Received: 02 April 2013

Accepted after revision: 07 May 2013

Publication Date:
07 June 2013 (online)


Abstract

A two-step, practical, regiospecific, and readily scalable benzannulation protocol for the preparation of novel 3-alkyl- and 3-aryl-substituted 2-nitronaphthalenes is disclosed. Addition of a β-nitrostyrene or nitroalkene to a solution of freshly prepared lithiated o-tolualdehyde tert-butyl imine first leads to the formation of a nitronate, via rapid 1,4-addition, then an intramolecular aza-Henry reaction takes place to afford a six-membered carbocycle. Subsequent treatment of the reaction mixture with aqueous acid affords novel substituted cyclic nitrostyrenes that can be conveniently aromatized via a one-pot radical-induced bromination and elimination sequence to furnish the corresponding 3-alkyl- or 3-aryl-2-nitronaphthalenes in excellent yields. The straightforward syntheses of 2-aminonaphthalenes, substituted BINAMs, 2-naphthols as well as tricyclic fused 1,2,3-triazoles are also described.

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