This minireview describes chemistry of hypervalent organoiodine triflates, which have received wide synthetic application as powerful electrophilic reagents and oxidants. The first representative of these compounds, μ-oxo-bis[(trifluoromethanesulfonato)(phenyl)iodine], was originally prepared and investigated in N. S. Zefirov's laboratory at Moscow State University in the early 1980s. This compound, now commonly known as Zefirov's reagent, is a useful reagent for the synthesis of various iodonium salts from the corresponding organic precursors. Recently, thermally stable and highly reactive triflates derived from cyclic hypervalent iodine compounds, benziodoxoles, have been reported and utilized in organic synthesis. The strongest iodine(V) oxidant, IBX-ditriflate, has been prepared from 2-iodoxybenzoic acid (IBX) and triflic acid. IBX-ditriflate can readily oxidize organic substrates that are generally resistant to oxidation. Zefirov's reagent and related hypervalent iodine triflates Zefirov's reagent and related hypervalent iodine triflates Publication Mendeleev Communications Record type Journal article Published May 2021 Authors Mekhman S. Yusubov | Viktor V. Zhdankin DOI https://doi.org/10.1016/j.mencom.2021.04.002 The publisher of this work supports multiple resolution . The work is available from the following locations: elsevier.com mathnet.ru debug {'doi': '10.1016/j.mencom.2021.04.002', 'member_id': '51372', 'member': 'OOO Zhurnal "Mendeleevskie Soobshcheniya"', 'container-title': 'Mendeleev Communications', 'primary-resource': 'https://linkinghub.elsevier.com/retrieve/pii/S0959943621001115', 'tld': 'elsevier.com', 'clearbit-logo': '/static/no_logo.svg', 'coaccess': [], 'multiple-resolution': [{'url': 'https://www.mathnet.ru/eng/mendc906', 'tld': 'mathnet.ru', 'clearbit-logo': '/static/no_logo.svg'}], 'type': 'JOURNAL ARTICLE', 'published_date': 'May 2021', 'publication': 'Mendeleev Communications', 'title': "Zefirov's reagent and related hypervalent iodine triflates", 'name': None, 'id': None, 'location': None, 'display_doi': 'https://doi.org/10.1016/j.mencom.2021.04.002', 'grant_info': None, 'grant_info_funders': None, 'grant_info_funder_ids': '', 'grant_info_type': None, 'multiple_lead_investigators': [], 'multiple_co_lead_investigators': [], 'multiple_investigators': [], 'finances': [], 'project_description': None, 'award_amount': None, 'award_start': None, 'funding_scheme': None, 'internal_award_number': None, 'editors': None, 'authors': 'Mekhman S.

Esters of 2-iodoxybenzoic acid (IBX-esters) were prepared by the hypochlorite oxidation of the corresponding 2-iodobenzoate esters and isolated as chemically stable, microcrystalline products. These hypervalent iodine compounds are potentially valuable oxidizing reagents belonging to a new class of pentavalent iodine compounds with a pseudobenziodoxole structure. Methyl 2-iodoxybenzoate can be further converted to the diacetate or a bis(trifluoroacetate) derivative by treatment with acetic anhydride or trifluoroacetic anhydride, respectively. Single-crystal X-ray diffraction analysis of methyl 2-[(diacetoxy)iodosyl]benzoate 8a reveals a pseudobenziodoxole structure with three relatively weak intramolecular I...O interactions. The dimethyl and diisopropyl esters of 2-iodoxyisophthalic acid were prepared by oxidation of the respective iodoarenes with dimethyldioxirane. Single-crystal X-ray diffraction analysis of diisopropyl 2-iodoxyisophthalate 6b showed intramolecular I...O interaction with the carbonyl oxygen of only one of the two carboxylic groups, while NMR spectra in solution indicated equivalency of both ester groups. IBX-esters, methyl 2-[(diacetoxy)iodosyl]benzoate, and 2-iodoxyisophthalate esters can oxidize alcohols to the respective aldehydes or ketones in the presence of trifluoroacetic acid or boron trifluoride etherate. The bis(trifluoroacetate) derivative can oxidize alcohols to carbonyl compounds without acid catalyst.