Domino Heck-Diels-Alder reactions of monosubstituted bicyclopropylidenes


Yucel B. , NOLTEMEYER M., DE MEIJERE A.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, no.6, pp.1072-1078, 2008 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Publication Date: 2008
  • Doi Number: 10.1002/ejoc.200700999
  • Title of Journal : EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
  • Page Numbers: pp.1072-1078

Abstract

A three-component domino Heck-Diels-Alder reaction involving pinacol bicyclopropylideneboronate (8b), iodobenzene (9) and methyl acrylate (12) under Jeffery conditions [Pd(OAc)(2), PPh(3), K(2)CO(3), Et(4)NCl, MeCN] produced a mixture of phenylspiro[2.5]octeneboronates syn/anti-(E)-14b and methyl phenylspirooctenecarboxylate 25 in 25 and 38 % yield, respectively. The major product 25 was most probably formed via the homoallylpalladium complex 23b undergoing deboropalladation rather than dehydropalladation. Similarly, reactions of tributylstannyl- and hydroxydimethylsilyl-substituted bicyclopropylidenes 8c-d with 9 and tert-butyl acrylate gave the tert-butyl phenylspirooctenecarboxylate 26 via the diene 24 formed by demetallopalladation processes. The reaction of methyl 1,1'-bicyclopropylidene-2-carboxylate (8e) with iodobenzene (9) in the presence of tert-butyl acrylate (13) furnished a mixture of regimsomeric and diastereomeric spirooctenes syn/anti-(E)-15e and syn/anti-(Z)-15e in 69 and 6 % yield, respectively. The structures of the major pair of diastereomers syn-(E)-15e and anti-(E)-15e were rigorously proved by X-ray crystal structure analyses.