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Synthesis 2011(19): 3152-3160  
DOI: 10.1055/s-0030-1260146
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Waste-Free Catalytic Propargylation/Allenylation of Aryl and Heteroaryl Nucleophiles and Synthesis of Naphthopyrans

J. Adam McCubbin*, Costa Nassar, Oleg V. Krokhin
Department of Chemistry, University of Winnipeg, 515 Portage Ave., Winnipeg, MB, R3B 2E9, Canada
Fax: +1(204)7752114; e-Mail: a.mccubbin@uwinnipeg.ca;
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Publication History

Received 16 June 2011
Publication Date:
01 August 2011 (online)

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Abstract

A general method for the substitution of propargylic alcohols with electron-rich aromatic carbocycles and heterocycles has been developed. The reaction occurs under simple, mild conditions, and employs an inexpensive environmentally benign and recoverable arylboronic acid catalyst, perfluorophenylboronic acid, producing water as the only byproduct. High yields and selectivities are observed for propargyl- or allenyl-substituted products, including furans, indoles, and pyrroles, as well as methoxy-substituted benzenes and naphthalenes. Reaction with 2-naphthol affords substituted naphthopyrans as products. Preliminary evidence suggests a Friedel-Crafts-like substitution mechanism, which occurs via an in situ generated carbocation.

Key words

organocatalysis - boronic acids - propargylic alcohols - Friedel-Crafts reaction

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