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Ring Expansion-Annulation Strategy for the Synthesis of Substituted Azulenes and Oligoazulenes. 2. Synthesis of Azulenyl Halides, Sulfonates, and Azulenylmetal Compounds and Their Application in Transition-Metal-Mediated Coupling Reactions

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Aimee L. Crombie, John L. Kane, Jr., Kevin M. Shea, and Rick L. Danheiser*

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139

J. Org. Chem., 2004, 69 (25), pp 8652–8667

DOI: 10.1021/jo048698c

Publication Date (Web): November 6, 2004

Section:

Alicyclic Compounds

Abstract

A “ring expansion-annulation strategy” for the synthesis of substituted azulenes is described based on the reaction of β‘-bromo-α-diazo ketones with rhodium carboxylates. The key transformation involves an intramolecular Büchner reaction followed by β-elimination of bromide, tautomerization, and in situ trapping of the resulting 1-hydroxyazulene as a carboxylate or triflate ester. Further synthetic elaboration of the azulenyl halide and sulfonate annulation products can be achieved by employing Heck, Negishi, Stille, and Suzuki coupling reactions. Reaction of the azulenyl triflate 84 with pinacolborane provides access to the azulenylboronate 91, which participates in Suzuki coupling reactions with alkenyl and aryl iodides. The application of these coupling reactions to the synthesis of biazulenes, terazulene 101, and related oligoazulenes is described, as well as the preparation of the azulenyl amino acid derivative 110.

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History

Published In Issue December 10, 2004
Received July 28, 2004

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Article

Ring Expansion-Annulation Strategy for the Synthesis of Substituted Azulenes and Oligoazulenes. 2. Synthesis of Azulenyl Halides, Sulfonates, and Azulenylmetal Compounds and Their Application in Transition-Metal-Mediated Coupling Reactions

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A Ring Expansion−Annulation Strategy for the Synthesis of Substituted Azulenes. Preparation and Suzuki Coupling Reactions of 1-Azulenyl Triflates

Asymmetric Sulfur Ylide Reactions with Boranes: Scope and Limitations, Mechanism and Understanding

The First Fully Characterized 1,3-Polyazulene: High Electrical Conductivity Resulting from Cation Radicals and Polycations Generated upon Protonation

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