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DOI: 10.1055/s-2004-834879
New Method for the Synthesis of Functionalized 1,3-Bis-Exocyclic Dienes via a Palladium-Catalyzed Reaction. Scope and Synthetic Applications
Publication History
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.
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1 Introduction
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2 Formation of Cyclopentanic Derivatives
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3 Formation of Cyclohexanic Derivatives
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3.1 Synthesis of 1,3-Bis-Exocyclic Dienes
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3.2 Synthesis of Conjugated Trienes
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4 Synthetic Applications
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4.1 Diels-Alder Reaction
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4.2 Intramolecular Friedel-Crafts Reaction
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4.3 Thermal Electrocyclization
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4.3.1 Reaction on Conjugated Exocyclic Trienes
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4.3.2 One-Pot Synthesis of Functionalized Cyclohexadienes
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5 Conclusion
Key words
palladium - cyclization - enynes - exocyclic dienes - electrocyclization
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15The 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.