Synthesis 2007(17): 2585-2607  
DOI: 10.1055/s-2007-983835
REVIEW
© Georg Thieme Verlag Stuttgart · New York

Oxidative Cyclization of Dienes and Polyenes Mediated by Transition-Metal-Oxo Species

Vincenzo Piccialli*Dipartimento di Chimica Organica e Biochimica, Università degli Studi di Napoli ‘Federico II’, Via Cynthia 4, 80126 Napoli, Italy
Fax: +39(081)674393; e-Mail: vinpicci@unina.it;
Further Information

Publication History

Received 24 April 2007
Publication Date:
08 August 2007 (eFirst)

Abstract

During the last forty years, several groups have reported results concerning the oxidative cyclization of polyenes, mostly dienes, with transition-metal-oxo species such as permanganate, ruthenium tetroxide, perruthenate and osmium tetroxide, but only recently has a systematic study of some of these processes been undertaken. The formation in a single step of tetrahydrofuran, poly-tetrahydrofuran, tetrahydropyran and oxepane products with complete relative stereocontrol, and the unique postulated mechanisms, render these processes very appealing from both the synthetic and theoretical points of view. Recent synthetic applications of these oxidative transformations have highlighted their usefulness. This review summarizes the state of the art in this field, in an attempt to provide a comprehensive view of these processes. Some similarities between the chemistry of ruthenium tetroxide and rhenium(VII)-oxo species are highlighted.

1 Introduction

2 Formation of Tetrahydrofurans

2.1 Permanganate-Mediated Cyclization of 1,5-Dienes

2.2 Ruthenium Tetroxide Catalyzed Cyclization of 1,5-Dienes

2.2.1 Synthetic Applications of Ruthenium Tetroxide Catalyzed Cyclization of 1,5-Dienes

2.3 Perruthenate-Catalyzed Cyclization of 1,5-Dienes

2.4 Osmium Tetroxide Catalyzed Cyclization of 1,4- and 1,5-Dienes

3 Osmium Tetroxide Catalyzed Formation of Tetrahydrofurans from Alkenediols

4 Osmium Tetroxide Catalyzed Formation of Pyrrolidines

5 Chromium(VI)-Mediated Formation of Tetrahydrofurans from Alkenediols

6 Formation of Tetrahydropyrans

6.1 Ruthenium Tetroxide Catalyzed Cyclization of 1,6-Dienes

6.2 Permanganate-Mediated Cyclization of 1,6-Dienes

7 Ruthenium Tetroxide Catalyzed Formation of Oxepanes from 1,7-Dienes

8 Ruthenium Tetroxide and Permanganate-Mediated Formation of Oxiranes from 1,3-Dienes

9 Ruthenium Tetroxide Catalyzed Oxidative Polycyclization

10 Conclusions