An Old Dog with New Tricks: Enjoin Wolff–Kishner Reduction for Alcohol Deoxygenation and C–C Bond Formations

Chao-Jun Li; Jianlin Huang; Xi-Jie Dai; Haining Wang; Ning Chen; Wei Wei; Huiying Zeng; Jianting Tang; Chenchen Li; Dianhu Zhu; Leiyang Lv

doi:10.1055/s-0037-1611853

Synlett, Table of Contents

Synlett 2019; 30(13): 1508-1524
DOI: 10.1055/s-0037-1611853

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An Old Dog with New Tricks: Enjoin Wolff–Kishner Reduction for Alcohol Deoxygenation and C–C Bond Formations

Chao-Jun Li*

Department of Chemistry and FQRNT Centre for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke Street West, Montreal, Quebec H3A 0B8, Canada Email: cj.li@McGill.ca

,

Jianlin Huang ◊

,

Xi-Jie Dai ◊

,

Haining Wang ◊

,

Ning Chen

,

Wei Wei ◊

,

Huiying Zeng ◊

,

Jianting Tang ◊

,

Chenchen Li ◊

,

Dianhu Zhu ◊

,

Leiyang Lv ◊

› Author Affiliations

Abstract

All articles of this category

^◊ The co-authors are based on the chronical order worked on this project

Abstract

The Wolff–Kishner reduction, discovered in the early 1910s, is a fundamental and effective tool to convert carbonyls into methylenes via deoxygenation under strongly basic conditions. For over a century, numerous valuable chemical products have been synthesized by this classical method. The reaction proceeds via the reversible formation of hydrazone followed by deprotonation with the strong base to give an N-anionic intermediate, which affords the deoxygenation product upon denitrogenation and protonation. By examining the mechanistic pathway of this century old classical carbonyl deoxygenation, we envisioned and subsequently developed two unprecedented new types of chemical transformations: a) alcohol deoxygenation and b) C–C bond formations with various electrophiles including Grignard-type reaction, conjugate addition, olefination, and diverse cross-coupling reactions.

1 Introduction

2 Background

3 Alcohol Deoxygenation

3.1 Ir-Catalyzed Alcohol Deoxygenation

3.2 Ru-Catalyzed Alcohol Deoxygenation

3.3 Mn-Catalyzed Alcohol Deoxygenation

4 Grignard-Type Reactions

4.1 Ru-Catalyzed Addition of Hydrazones with Aldehydes and Ketones

4.2 Ru-Catalyzed Addition of Hydrazone with Imines

4.3 Ru-Catalyzed Addition of Hydrazone with CO₂

4.4 Fe-Catalyzed Addition of Hydrazones

5 Conjugate Addition Reactions

5.1 Ru-Catalyzed Conjugate Addition Reactions

5.2 Fe-Catalyzed Conjugate Addition Reactions

6 Cross-Coupling Reactions

6.1 Ni-Catalyzed Negishi-type Coupling

6.2 Pd-Catalyzed Tsuji–Trost Alkylation Reaction

7 Other Reactions

7.1 Olefination

7.2 Heck-Type Reaction

7.3 Ullmann-Type Reaction

8 Conclusion and Outlook

Keywords

alkylation - carbanions - catalysis - cross-coupling - deoxygenation - Grignard reaction - hydrazones - nucleophilic addition

Full Text

References

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