Ionic Transfer Reactions with Cyclohexadiene-Based Surrogates

Johannes C. L. Walker; Martin Oestreich

doi:10.1055/s-0039-1690233

Synlett, Table of Contents

Synlett 2019; 30(20): 2216-2232
DOI: 10.1055/s-0039-1690233

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Ionic Transfer Reactions with Cyclohexadiene-Based Surrogates

Johannes C. L. Walker

,

Martin Oestreich ∗

Abstract

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Abstract

A current research program in our laboratory is devoted to the development of cyclohexa-1,4-diene-based surrogates of difficult-to-handle compounds and their application in metal-free ionic transfer reactions. These investigations grew from our interest in silylium ion chemistry and consequently concentrated initially on surrogates of gaseous and explosive hydrosilanes such as Me₃SiH and even monosilane (SiH₄). Since then, we have expanded the concept to design surrogates of other species including H₂, mineral acids (HI and HBr), and hydrocarbons (isobutane and isobutene). This Account summarizes our discoveries in this area to date, describing the challenges we faced along the way and how we combatted them.

1 Introduction

2 Transfer Hydrofunctionalization: Variation of the Electrofuge

3 Transfer Hydrofunctionalization: Variation of the Nucleofuge

4 Transfer Hydrohalogenation Using a Modified Surrogate

5 Surrogate Synthesis

6 Conclusion

Key words

ionic transfer chemistry - main-group catalysis - metal-free - surrogates - Wheland intermediates

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References

References and Notes

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