New Methods in Organic Synthesis Through Copper-Catalyzed Borylation Reactions: Stereoselective Synthesis of 1,4-Diols and Vinylboronates

Ricardo Alfaro; Alejandro Parra; José Alemán; Mariola Tortosa

doi:10.1055/s-0032-1318483

Synlett, Table of Contents

Synlett 2013; 24(7): 804-812
DOI: 10.1055/s-0032-1318483

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New Methods in Organic Synthesis Through Copper-Catalyzed Borylation Reactions: Stereoselective Synthesis of 1,4-Diols and Vinylboronates

Ricardo Alfaro

Departamento de Química Orgánica (módulo 01), Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain Fax: +34(91)4973966 Email: mariola.tortosa@uam.es

,

Alejandro Parra

Departamento de Química Orgánica (módulo 01), Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain Fax: +34(91)4973966 Email: mariola.tortosa@uam.es

,

José Alemán

Departamento de Química Orgánica (módulo 01), Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain Fax: +34(91)4973966 Email: mariola.tortosa@uam.es

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Mariola Tortosa*

Departamento de Química Orgánica (módulo 01), Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain Fax: +34(91)4973966 Email: mariola.tortosa@uam.es

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Abstract

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In memory of Christian G. Claessens

Abstract

Boronic acid derivatives have become important intermediates in organic and medicinal chemistry and, as a result, the development of new methods that permit the efficient creation of C–B bonds under mild conditions has become an active field of research in organic synthesis. In the last ten years, copper-catalyzed borylation reactions have emerged as versatile new tools for introducing boron atoms into organic molecules. Here, we describe our recent research in this field. We have developed two copper-catalyzed borylation reactions. The first involves the S_N2′ addition of bis(pinacolato)diboron to allylic epoxides. This reaction permits the stereoselective synthesis of a wide range of compounds containing a 1,4-diol moiety, a fragment that is present in many natural products with important biological activities. The second reaction is a copper-catalyzed formal carboboration process. In this reaction, a C–B and a C–C bond are created in a single catalytic cycle, and the method provides a new tool for the synthesis of tri- and tetrasubstituted vinylboronates.

1 Introduction

2 Stereoselective Synthesis of 1,4-Diols

3 Synthesis of Tri- and Tetrasubstituted Vinylboronates

4 Outlook

Key words

boron - esters - copper - catalysis - diols - alkenes - carboborations

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References

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