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 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 73 Issue: 4
  • Publication Date: 2017
  • Doi Number: 10.1016/j.tet.2016.11.061
  • Title of Journal : TETRAHEDRON
  • Page Numbers: pp.291-297


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.