Nickel-catalyzed denitrogenative annulation reactions of 1,2,3-benzotriazin-4(3H)-ones with 1,3-dienes and alkenes

Tomoya Miura; Masao Morimoto; Motoshi Yamauchi; Masahiro Murakami

doi:10.1021/jo1008756

Nickel-catalyzed denitrogenative annulation reactions of 1,2,3-benzotriazin-4(3H)-ones with 1,3-dienes and alkenes

J Org Chem. 2010 Aug 6;75(15):5359-62. doi: 10.1021/jo1008756.

Authors

Tomoya Miura¹, Masao Morimoto, Motoshi Yamauchi, Masahiro Murakami

Affiliation

¹ Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto 615-8510, Japan.

PMID: 20604510
DOI: 10.1021/jo1008756

Abstract

1,2,3-Benzotriazin-4(3H)-ones react with 1,3-dienes in the presence of a nickel(0)/phosphine complex to give a variety of 3,4-dihydroisoquinolin-1(2H)-ones. Oxidative insertion of nickel(0) into the triazinone moiety prompts extrusion of dinitrogen to give a five-membered ring azanickelacyclic intermediate. Subsequent insertion of 1,3-dienes into the nickel-carbon bond followed by allylic amidation affords 3,4-dihydroisoquinolin-1(2H)-ones. Alkenes also undergo insertion into the five-membered ring azanickelacyclic intermediate, and subsequent reductive elimination gives 3-substituted 3,4-dihydroisoquinolin-1(2H)-ones.