Propargylic activation across a heterobimetallic ir-sn catalyst: nucleophilic substitution and indene formation with propargylic alcohols

Paresh Nath Chatterjee; Sujit Roy

doi:10.1021/jo100189z

Propargylic activation across a heterobimetallic ir-sn catalyst: nucleophilic substitution and indene formation with propargylic alcohols

J Org Chem. 2010 Jul 2;75(13):4413-23. doi: 10.1021/jo100189z.

Authors

Paresh Nath Chatterjee¹, Sujit Roy

Affiliation

¹ Organometallics and Catalysis Laboratory, Chemistry Department, Indian Institute of Technology, Kharagpur 721302, India.

PMID: 20536144
DOI: 10.1021/jo100189z

Abstract

A nucleophilic substitution of propargylic alcohols with carbon (arene, heteroarene, and allyltrimethylsilane), sulfur (thiol), oxygen (alcohol), and nitrogen (sulfonamide) nucleophiles has been demonstrated using a high-valent [Ir(COD)(SnCl(3))Cl(mu-Cl)](2) catalyst in 1,2-dichloroethane to afford the corresponding propargylic products in moderate to excellent yields. Alkyl or aryl substituted tertiary propargylic alcohols produce substituted indenes with bulky arenes via allenylic intermediate. An electrophilic mechanism is proposed from Hammett correlation.