Synlett 2019; 30(13): 1508-1524
DOI: 10.1055/s-0037-1611853
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© Georg Thieme Verlag Stuttgart · New York

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 ◊
,
,
Wei Wei ◊
,
Huiying Zeng ◊
,
Jianting Tang ◊
,
Chenchen Li ◊
,
Dianhu Zhu ◊
,
Leiyang Lv ◊
› Institutsangaben
We thank the Canada Research Chair (Tier I) foundation, the Canada Foundation for Innovation, Natural Sciences and Engineering Research Council of Canada, Fonds Québécois de la Recherche sur la Nature et les Technologies, McGill University and the Canadian Council of Arts (Killam Research Fellow Program) for support of our research We also thank the China Scholarship Council, China Postdoctoral Foundation, Shanghai Institute of Organic chemistry (CAS), and the Quebec Merit Fellowships for Foreign Postdoc (PBEEE) for supporting the co-authors.
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Publikationsverlauf

Received: 23. März 2019

Accepted after revision: 14. Mai 2019

Publikationsdatum:
13. Juni 2019 (online)


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