Synthesis 2017; 49(24): 5307-5319
DOI: 10.1055/s-0036-1589102
short review
© Georg Thieme Verlag Stuttgart · New York

Electrophilic Ring Opening of Small Heterocycles

Chuan Wang*
Department of Chemistry, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui, 230026, P. R. of China   Email: chuanw@ustc.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 14 July 2017

Accepted after revision: 01 August 2017

Publication Date:
30 August 2017 (online)


Abstract

Small heterocycles, such as epoxides, aziridines, and ox­etanes are among the most useful building blocks in organic synthesis. Through electrophilic ring opening of these molecules, various electrophilic functional groups can be installed, which cannot be achieved via classic nucleophilic ring-opening reactions. In this review, the developments of electrophilic ring opening of small heterocycles are surveyed and organized according to the types of metal promoters.

1 Introduction

2 Electrophilic Ring Opening of Small Heterocycles Using Stoichiometric Metals

2.1 Lithium-Mediated Electrophilic Ring Opening of Epoxides and Oxetanes

2.2 Chromium-Mediated Electrophilic Ring Opening of Vinyl Epoxides

2.3 Tin-Mediated Electrophilic Ring Opening of Vinyl Epoxides

2.4 Samarium-Mediated Electrophilic Ring Opening of Vinyl and Alkynyl Epoxides

2.5 Titanium-Mediated Electrophilic Ring Opening of Epoxides

2.6 Platinum, Palladium, and Nickel-Mediated Electrophilic Ring Opening of 1,1-Dimethyl Ethylene Oxide

3 Catalytic Electrophilic Ring Opening of Small Heterocycles

3.1 Titanium-Catalyzed Electrophilic Ring Opening of Epoxides

3.2 Palladium-Catalyzed Electrophilic Ring Opening of Vinyl and Alkynyl Small Heterocycles

3.3 Iron-Catalyzed Electrophilic Ring Opening of Oxetanes

3.4 Scandium-Catalyzed Electrophilic Ring Opening of Vinyl Epoxides

3.5 Iridium-Catalyzed Electrophilic Ring Opening of 2-Methyl 2-Vinyl­oxiranes

3.6 Nickel-Catalyzed Electrophilic Ring Opening of Epoxides and Aziridines

3.7 Nickel–Titanium-Cocatalyzed Electrophilic Ring Opening of Epoxides

4 Summary