Benziodoxole-Derived Organosulfonates: The Strongest Hypervalent Iodine Electrophiles and Oxidants

Mekhman S. Yusubov; Pavel Postnikov; Akira Yoshimura; Viktor V. Zhdankin

doi:10.1055/s-0039-1690761

Synlett, Table of Contents

Synlett 2020; 31(04): 315-326
DOI: 10.1055/s-0039-1690761

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Benziodoxole-Derived Organosulfonates: The Strongest Hypervalent Iodine Electrophiles and Oxidants

Mekhman S. Yusubov

^aResearch School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, 634050 Tomsk, Russian Federation

,

Pavel Postnikov

^aResearch School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, 634050 Tomsk, Russian Federation

,

Akira Yoshimura

^aResearch School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, 634050 Tomsk, Russian Federation

,

Viktor V. Zhdankin ∗

^bDepartment of Chemistry and Biochemistry, University of Minnesota Duluth, Duluth, MN 55812, USA Email: vzhdanki@d.umn.edu

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Abstract

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Abstract

This account describes the development of organosulfonyloxy-substituted iodine(III) and iodine(V) benziodoxole derived reagents, which are thermally stable compounds with useful reactivity patterns. Iodine(III) benziodoxoles and pseudobenziodoxoles are powerful electrophiles and mild oxidants toward various unsaturated compounds. In particular, pseudocyclic benziodoxole-derived triflate (IBA-OTf) is an efficient reagent for oxidative heteroannulation reactions. Aldoximes react with nitriles in the presence of IBA-OTf at room temperature to give 1,2,4-oxadiazoles in high yields. Moreover, IBA-triflate is used as a catalyst in oxidative heteroannulations with m-chloroperoxybenzoic acid as the terminal oxidant. The iodine(V) benziodoxole derived tosylates, DMP-tosylate and IBX-tosylate, are superior oxidants for the oxidation of structurally diverse, synthetically useful alcohols, utilized as key precursors in the total syntheses of polyketide antibiotics and terpenes. And finally, the most powerful hypervalent iodine(V) oxidant, 2-iodoxybenzoic acid ditriflate (IBX·2HOTf), is prepared by treatment of IBX with trifluoromethanesulfonic acid. According to the X-ray data, the I–OTf bonds in IBX-ditriflate have ionic character, leading to the high reactivity of this reagent in various oxidations. In particular, IBX-ditriflate can oxidize polyfluorinated primary alcohols, which are generally extremely resistant to oxidation.

1 Introduction

2 Iodine(III) Benziodoxole Based Organosulfonates

3 Pseudocyclic Iodine(III) Benziodoxole Triflate (IBA-triflate)

4 Pseudocyclic Iodine(III) Benziodoxole Tosylates

5 Iodine(V) Benziodoxole Derived Tosylates

6 Iodine(V) Benziodoxole Derived Triflate (IBX-ditriflate)

7 Conclusions

Key words

hypervalent iodine - iodine - iodonium - 2-iodosylbenzoic acid (IBA) - 2-iodoxybenzoic acid (IBX) - oxidation

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References

References
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