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Synthesis 2018; 50(15): 2824-2852
DOI: 10.1055/s-0036-1589535
review
© Georg Thieme Verlag Stuttgart · New York

Acetonitrile as a Building Block and Reactant

B. H. Hoff*
Department of Chemistry, Norwegian University of Science and Technology (NTNU), Høgskoleringen 5, 7491 Trondheim, Norway   Email: Bard.Helge.Hoff@chem.ntnu.no
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Further Information

Publication History

Received: 20 March 2018

Accepted after revision: 19 April 2018

Publication Date:
13 June 2018 (online)

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Abstract

Acetonitrile is popular as a solvent for performing organic reactions, as a ligand in inorganic chemistry, as a mobile phase in chromatography, and as an electrolyte solvent in dye-sensitized solar cells. This is mainly due to its ability to dissolve both polar and nonpolar components. However, acetonitrile is also a valuable building block allowing atom-efficient transformations in synthetic organic chemistry. The aim of this review is to highlight synthetic transformations using acetonitrile, covering both classical approaches and modern strategies proceeding through radical intermediates or mediated by metal catalysis. Besides showcasing synthetic protocols useful for acetonitrile and analogues, warnings for when not to use acetonitrile as a solvent are also provided.

1 Introduction

2 Fundamental Reactions with Acetonitrile

3 Cyanomethylation of Non-Aromatics

4 The Acetonitrile Nitrogen as a Nucleophile

5 The Blaise Reaction

6 Synthesis of Pyridines

7 Other Cyclization Reactions

8 Cyanomethylation of Arenes and Heteroarenes

9 Acetylation of Arenes Using Acetonitrile

10 Synthesis of N-Arylacetamides

11 Cyanation Using Acetonitrile as a Cyanide Source

12 When To Avoid Acetonitrile as a Solvent

13 Conclusion

Key words

acetonitrile - cyanomethylation - cyanation - cyclotrimerization - Cu catalysis - Ritter reaction - pyridine synthesis