Deoxygenative Transition-Metal-Promoted Reductive Coupling and Cross-Coupling of Alcohols and Epoxides

Abstract

The prospective utilization of abundant, CO₂-neutral, renewable feedstocks is driving the discovery and development of new reactions that refunctionalize oxygen-rich substrates such as alcohols and polyols through C–O bond activation. In this review, we highlight the development of transition-metal-promoted reactions of renewable alcohols and epoxides that result in carbon–carbon bond-formation. These include reductive self-coupling reactions and cross-coupling reactions of alcohols with alkenes and arene derivatives. Early approaches to reductive couplings employed stoichiometric amounts of low-valent transition-metal reagents to form the corresponding hydrocarbon dimers. More recently, the use of redox-active transition-metal catalysts together with a reductant has enhanced the practical applications and scope of the reductive coupling of alcohols. Inclusion of other reaction partners with alcohols such as unsaturated hydrocarbons and main-group organometallics has further expanded the diversity of carbon skeletons accessible and the potential for applications in chemical synthesis. Catalytic reductive coupling and cross-coupling reactions of epoxides are also highlighted. Mechanistic insights into the means of C–O activation and C–C bond formation, where available, are also highlighted.

1 Introduction

2 Stoichiometric Reductive Coupling of Alcohols

3 Catalytic Reductive Coupling of Alcohols

3.1 Heterogeneous Catalysis

3.2 Homogeneous Catalysis

4 Reductive Cross-Coupling of Alcohols

4.1 Reductive Alkylation

4.2 Reductive Addition to Olefins

5 Epoxide Reductive Coupling Reactions

6 Conclusions and Future Directions

Key words

renewable feedstocks - alcohols - epoxides - transition-metal catalysts - reductive coupling - cross-coupling

Publication History

Received: 24 June 2020

Accepted after revision: 04 August 2020

Article published online:
07 October 2020

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