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Synthesis 2005(2): 311-329  
DOI: 10.1055/s-2004-834879
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart · New York

New Method for the Synthesis of Functionalized 1,3-Bis-Exocyclic Dienes via a Palladium-Catalyzed Reaction. Scope and Synthetic Applications

Thierry Lomberget, Didier Bouyssi, Geneviève Balme*
Laboratoire de Chimie Organique 1, associé au CNRS, Université Claude Bernard Lyon 1, CPE, 43 Bd du 11 Novembre 1918, 69622 Villeurbanne, France
Fax: +33(4)72431214; e-Mail: balme@univ-lyon1.fr;
Further Information

Publication History

Received 26 April 2004
Publication Date:
21 October 2004 (online)

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Abstract

The palladium-catalyzed tandem cyclization-coupling reaction of conjugated enynes having a stabilizing carbon nucleophile with aryl iodides and vinyl halides or triflates produced stereo­defined, functionalized five- and six-membered 1,3-bis-exocyclic dienes in moderate to good yields. These stereodefined dienes proved to be versatile substrates for the preparation of various polycyclic products through subsequent Diels-Alder, intramolecular Friedel-Crafts or thermal electrocyclization reactions.

  • 1 Introduction

  • 2 Formation of Cyclopentanic Derivatives

  • 3 Formation of Cyclohexanic Derivatives

  • 3.1 Synthesis of 1,3-Bis-Exocyclic Dienes

  • 3.2 Synthesis of Conjugated Trienes

  • 4 Synthetic Applications

  • 4.1 Diels-Alder Reaction

  • 4.2 Intramolecular Friedel-Crafts Reaction

  • 4.3 Thermal Electrocyclization

  • 4.3.1 Reaction on Conjugated Exocyclic Trienes

  • 4.3.2 One-Pot Synthesis of Functionalized Cyclohexadienes

  • 5 Conclusion

Key words

palladium - cyclization - enynes - exocyclic dienes - electrocyclization

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7

The palladium(0)-diphenylphosphinoethane was preformed by heating Pd(OAc)2 (5 mol%) and dppe (5 mol%) in the presence of 1-heptene (10 mol%, THF 50 °C) until a homogeneous dark red solution was obtained.

15

The stereochemistry of the substituted double bond is defined by the mechanism of the Wacker-type reaction. [2] The E configuration of 7a was confirmed by a NOESY experiment in the 1H NMR.