Synlett 2010(20): 2973-2988  
DOI: 10.1055/s-0030-1259071
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Electrophilic Functionalization of Non-Activated Olefins Catalyzed by Lewis Superacids

Sylvain Antoniotti, Sophie Poulain-Martini, Elisabet Duñach*
Laboratoire de Chimie des Molécules Bioactives et des Arômes, Université de Nice-Sophia Antipolis, CNRS-UMR 6001, Institut de Chimie de Nice, 28 Av. Valrose, 06108 Nice, France
Fax: +33(4)92076151; e-Mail: dunach@unice.fr;
Further Information

Publication History

Received 28 July 2010
Publication Date:
24 November 2010 (online)

Abstract

The use of metallic triflates and triflimidates as efficient catalysts in recent cycloisomerizations, hydroalkoxylations, hydrocarboxylations, hydrothiolations, Friedel-Crafts reactions, α-amidoalkylation and other C-C, C-O and C-S coupling reactions is reviewed.

1 Introduction

2 Preparation of Metallic Triflates and Triflimidates

2.1 Preparation from Oxides, Halides, Carbonates, and Relatives

2.2 Electrochemical Method

2.3 Oxidative Dissolution of Metallic Powders in the Presence of Superacids

3 Formation of C-C Bonds

3.1 Diels-Alder-Type Reactions

3.2 [3+2] And [2+2] Cycloadditions

3.3 Diene and Polyprenoid Cycloisomerizations

3.4 Friedel-Crafts Reactions

3.4.1 Acylation of Arenes

3.4.2 Alkylation/Benzylation of Arenes

3.4.3 Friedel-Crafts Allylation

3.4.4 Tandem Allylation-Cyclization Processes

3.5 Addition of Nucleophiles to α-Hydroxylactams via N-Acyliminium Ion Intermediates

4 Formation of C-O Bonds

4.1 Intramolecular Hydroalkoxylation of Olefins

4.2 Intermolecular Hydroalkoxylation of Olefins

4.3 Intramolecular Hydrocarboxylation of Olefins

4.4 Dealkylative Cyclization of Epoxy Esters

4.5 Intramolecular Cyclization of Unsaturated Oximes

5 Formation of C-S Bonds

5.1 Intra- and Intermolecular Electrophilic Addition of RSH and RCOSH to Olefins

5.2 Isomerization of Thionolactones to Thiolactones

6 Outlook and Future Prospects