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Synlett 2022; 33(07): 617-636
DOI: 10.1055/s-0040-1719852
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Recent Advances in the Synthesis of Diverse Libraries of Small-Molecule Building Blocks in Ionic Liquids (ILs)

Kenneth K. Laali  ∗
a   Department of Chemistry, University of North Florida, 1, UNF Drive, Jacksonville, Florida 32224, USA
,
Rajesh G. Kalkhambkar∗
b   Department of Chemistry, Karnatak University’s Karnatak Science College, Dharwad, Karnatak 580001, India
,
Suraj M. Sutar
b   Department of Chemistry, Karnatak University’s Karnatak Science College, Dharwad, Karnatak 580001, India
› Author AffiliationsK.K.L. thanks University of North Florida (UNF) for the Outstanding Faculty Scholarship and Presidential Professorship awards, UNF Foundation Board grant, and the Dean’s Leadership Council award. R.G.K. thanks the Department of Science and Technology, Science and Engineering Research Board (DST-SERB, Grant Number SB/FT/CS-175/2013), the University Grants Commission, South-Western Regional Office (UGC-SWRO, Grant Number 2069- MRP/15-16/KAKA056/UGC-SWRO), and the Vision Group on Science and Technology (VGST, Grant Number VGST-RGS/F/GRD-742/2017-18/2018-19) for providing financial assistance to complete various projects successfully. S.M.S. thanks Karnatak University and Karnatak Science College, Dharwad for university research studentship.
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Abstract

The Account describes recent advances, from the authors’ laboratories, in the synthesis of diverse libraries of small-molecule building blocks employing ionic liquids (ILs). The ability of ILs to act as catalysts/promoters/solvents for electrophilic and onium ion chemistry, as well as in metal-mediated cross-coupling reactions, and the potential to sequence/hyphenate these methods, have opened up new opportunities for facile assembly of functional small molecules with increased complexity from readily available precursors. While Brønsted acidic IL/IL solvent mixtures are suitable media for carbocation and onium ion chemistry, piperidine-appended IL/IL solvent mixtures can successfully catalyze a variety of base-catalyzed reactions. Several widely practiced transformations including ‘name reactions’ were adapted and performed efficiently in ILs.

1 Introduction

2 Aryldiazonium Salts and Aryltriazenes as Coupling Partners in Metal-Mediated C–C Cross-Coupling Reactions in ILs

3 Expanding the Scope of Metal-Mediated Cross-Coupling Reactions in ILs

4 Application of ILs in Synthesis and Functionalization of Hetero­cycles

5 Expanding the Scope of Amide Synthesis in ILs

6 Generation and Chemistry of ‘Tamed’ Propargylic Cations in ILs

7 Newer Nitration Methods for Arenes and Heteroarenes in ILs

8 Halofunctionalization in ILs

9 ‘Name Reactions’and Other Widely Practiced Synthetic Transformations in ILs

9.1 The Biginelli Reaction

9.2 Nitrile Synthesis by the Schmidt Reaction

9.3 Rupe Rearrangement

9.4 Synthesis of 1,3-Dioxanes via Prins Reaction in [BMIM(SO3H)][OTf]

9.5 Synthesis of Cyclopropanes and Oxiranes by the Corey–Chaykovsky (CC) Reaction

10 Conclusions and Closing Remarks

Key words

acidic and basic ionic liquids - aryldiazonium and aryltri­azene - cross-coupling - heterocyclic chemistry - sequential/hyphenated reactions


Publication History

Received: 17 August 2021

Accepted after revision: 06 October 2021

Article published online:
18 November 2021

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