Carbon–Carbon Bond Formation through Palladium Homoenolates

Nisha Nithiy; David Rosa; Arturo Orellana

doi:10.1055/s-0033-1340045

Synthesis, Table of Contents

Synthesis 2013; 45(23): 3199-3210
DOI: 10.1055/s-0033-1340045

short review

Carbon–Carbon Bond Formation through Palladium Homoenolates

Nisha Nithiy

Department of Chemistry, York University, 4700 Keele Street, Toronto, ON, M3J 1P3, Canada Fax: +1(416)7365936 Email: aorellan@yorku.ca

,

David Rosa

Department of Chemistry, York University, 4700 Keele Street, Toronto, ON, M3J 1P3, Canada Fax: +1(416)7365936 Email: aorellan@yorku.ca

,

Arturo Orellana*

Department of Chemistry, York University, 4700 Keele Street, Toronto, ON, M3J 1P3, Canada Fax: +1(416)7365936 Email: aorellan@yorku.ca

› Author Affiliations

Abstract

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Abstract

Homoenolates represent a useful class of umpolung synthons with the potential to greatly streamline complex molecule synthesis. Because the direct formation of homoenolates faces many limitations, a number of alternative approaches to this synthon have been developed. In this review we present the main strategies for the generation and application of palladium homoenolates. We highlight the merits and limitations of each approach, and comment on aspects of the mechanism of these reactions where appropriate.

1 Introduction

1.1 Palladium Homoenolates

1.2 Scope of this Review

2 Generation of Palladium Homoenolates via Transmetalation of Pre-Formed Homoenolates

2.1 Transmetalation of Zinc Homoenolates

2.2 Transmetalation of Boron Homoenolates

2.3 Transmetalation of Indium Homoenolates

3 Catalytic Generation of Palladium Homoenolates by Ring Cleavage of Cyclopropanol Derivatives

4 Generation of Homoenolates via Palladium-Catalyzed C–H Activation

5 Generation of Homoenolates via Palladium-Catalyzed Isomerization of Enolates

6 Conclusions and Outlook

Key words

umpolung - homoenolate - palladium - C–H activation - cyclopropane - transmetalation

Full Text

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