Alkene versus Aryl Chlorination in Asymmetric Hypervalent Iodine Catalysis: A Case Study

Andreas M. Arnold; Julia Binder; Martin Kretzschmar; Tanja Gulder

doi:10.1055/a-2201-7326

Synlett, Table of Contents

Synlett 2024; 35(09): 1001-1006
DOI: 10.1055/a-2201-7326

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Chemical Synthesis and Catalysis in Germany

Alkene versus Aryl Chlorination in Asymmetric Hypervalent Iodine Catalysis: A Case Study

Authors

Andreas M. Arnold

^aInstitute of Organic Chemistry, Leipzig University, Johannisallee 29, 04103 Leipzig, Germany

^bDepartment of Chemistry, Technical University of Munich, Lichtenbergstraße 4, 85748 Garching, Germany
Julia Binder

^aInstitute of Organic Chemistry, Leipzig University, Johannisallee 29, 04103 Leipzig, Germany

^bDepartment of Chemistry, Technical University of Munich, Lichtenbergstraße 4, 85748 Garching, Germany
Martin Kretzschmar

^aInstitute of Organic Chemistry, Leipzig University, Johannisallee 29, 04103 Leipzig, Germany
Tanja Gulder ∗

^aInstitute of Organic Chemistry, Leipzig University, Johannisallee 29, 04103 Leipzig, Germany

^bDepartment of Chemistry, Technical University of Munich, Lichtenbergstraße 4, 85748 Garching, Germany

Abstract

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Abstract

Hypervalent λ³-iodanes have become a prominent tool for halofunctionalizations of alkenes. Despite many examples of asymmetric fluorinations reported lately, the corresponding enantioselective chlorination reactions using iodoresorcinol-based catalysts are significantly less developed, with only one example known to date. Here, we show how competing aromatic chlorination of the iodoarene catalyst is a significant obstacle in these transformations, hinting towards a conceptual issue with this well-established catalyst class for enantioselective chlorinations. Consequently, the reaction conditions and the catalyst design must be adapted to facilitate an effective chirality transfer. Hence, attention should be paid when selecting the oxidizing agent, the stoichiometry, and careful reaction analysis must be conducted to identify the factual catalytically active species.

Key words

chlorination - hypervalent iodane catalysis - asymmetric reactions - iodoresorcinols - rearrangement

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References

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Supplementary Material

Supporting Information (PDF)