Synthesis of Cyclopentacarbazolones via Palladium-Catalyzed Annulation of Internal Alkynes

Abstract

A simple and efficient protocol for the synthesis of highly substituted cyclopentacarbazolones (50-82%) was developed by employing internal alkynes with 2-bromo-3-formylcarbazoles in the presence of palladium catalyst under ligand-free condition. High regioselectivity was observed for unsymmetrical (alkyl-, aryl-­substituted) internal alkynes.

estrogen receptors - palladium catalyst - annulations - cyclopentacarbazolones - ligand-free synthesis

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X-ray crystallographic data for 3a: Formula: C₃₀H₂₃N₁O₁. Unit cell parameters: a = 9.0690(13), b = 10.359(2), c = 13.357(2), α = 85.794(15), β = 72.369(13), γ = 70.831(16), space group P1. X-ray crystallographic data for 3r: Formula: C₂₆H₂₃N₁O₁. Unit cell parameters: a = 8.3997(16), b = 10.227(2), c = 12.402(2), α = 76.514(3), β = 78.141(3), γ = 75.769(3), space group P1. X-ray crystallographic data for 3s: Formula: C₂₅H₂₁N₁O₁. Unit cell parameters: a = 7.9184(6), b = 10.4371(7), c = 12.1136(10), α = 76.338(6), β = 83.212(7), γ = 77.905(6), space group P1. The CCDC deposition numbers of compounds 3a,r,s are 840023, 840025, and 840024, respectively. Further data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: [phone], E-mail: [e-mail]].