Synthesis 2001(8): 1258-1262
DOI: 10.1055/s-2001-15061
PAPER
© Georg Thieme Verlag Stuttgart · New York

Photochemical Synthesis of 3,4-Dihydro-2H-1,3-oxazin-4-ones

Pablo Wessig*, Jutta Schwarz, Ute Lindemann, Max C. HolthausenInstitut für Organische und Bioorganische Chemie, Humboldt-Universität zu Berlin, Hessische Straße 1-2, 10115 Berlin
Fax: +49(30)20936940; e-Mail: pablo = wessig@chemie.hu-berlin.de;
Further Information

Publication History

Received 5 February 2001
Publication Date:
24 September 2004 (online)

Abstract

The first example of a C-O bond formation in the course of the Norrish-Yang reaction is described. Starting with readily accessible α-mesyloxy-β-keto amides 4, a δ-hydrogen transfer to the excited carbonyl group occurs and the diradicals thus formed undergo a very rapid elimination of methane sulfonic acid providing enolate diradicals. These ambidental enolate diradicals undergo a regioselective cyclization to 3,4-dihydro-2H-1,3-oxazin-4-ones 5. In two cases a cleavage reaction is observed, giving cyclic imines. The mechanism is investigated by means of DFT- and ab initio methods.