Unusual manganese(III)-mediated oxidative free-radical additions of Meldrum's acid and dimethyl malonate to benzonorbornadiene and oxabenzonorbornadiene


ÇALIŞKAN R., Nohut N., Yilimaz O., ŞAHİN E., BALCI M.

TETRAHEDRON, vol.73, no.4, pp.291-297, 2017 (Peer-Reviewed Journal) identifier identifier

  • Publication Type: Article / Article
  • Volume: 73 Issue: 4
  • Publication Date: 2017
  • Doi Number: 10.1016/j.tet.2016.11.061
  • Journal Name: TETRAHEDRON
  • Journal Indexes: Science Citation Index Expanded, Scopus
  • Page Numbers: pp.291-297
  • Keywords: Manganase(III) acetate, Copper(II) acetate, Cycloaddition, Oxidation, Dihydrofurans, Rearrangement, Benzonorbornadiene, Oxabenzonorbornadiene, 1,3-DICARBONYL COMPOUNDS, METAL-SALTS, ACETATE, CYCLIZATIONS, DIHYDROFURANS, DERIVATIVES, MECHANISMS, MN(OAC)(3), ALKENES, KETONES

Abstract

Benzonorbornadiene and 7-oxabenzonorbornadiene were reacted with Meldrum's acid and dimethyl malonate in the presence of Mn(OAc)(3) and Cu(OAc)(2) in acetic acid. The reaction of benzonorbornadiene with Meldrum's acid gave a naphthalene derivative whereas the reaction with dimethyl malonate formed rearranged products derived from a carbocation intermediate. However, the reaction of 7-oxabenzonorbornadiene with Meldrum's acid gave two nonrearranged products. On the other hand, the reaction with dimethyl malonate unexpectedly formed a dihydronapthalene derivative with an unusual structure. The mechanism for the formation of the products is discussed. (C) 2016 Elsevier Ltd. All rights reserved.