35380-52-0

Upstream product

• 30989-24-3 bis(O-iodobenzoyl) peroxide 
• 609-67-6 2-Iodobenzoyl chloride 
• 1829-26-1 1-acetoxy-1,2-benziodoxol-3-one 
• 88-67-5 2-Iodobenzoic acid 
• 160732-56-9 1-azido-1λ³-benzo[d][1,2]iodaoxol-3(1H)-one 

Relevant academic research and scientific papers

Mechanistic Investigation of the Iron-Catalyzed Azidation of Alkyl C(sp3)-H Bonds with Zhdankin’s λ3-Azidoiodane

An in-depth study of the mechanism of the azidation of C(sp3)-H bonds with Zhdankin’s λ3-azidoiodane reagent catalyzed by iron(II)(pybox) complexes is reported. Previously, it was shown that tertiary and benzylic C(sp3)-H bonds of a range of complex molecules underwent highly site-selective azidation by reaction with a λ3-azidoiodane reagent and an iron(II)(pybox) catalyst under mild conditions. However, the mechanism of this reaction was unclear. Here, a series of mechanistic experiments are presented that reveal critical features responsible for the high selectivity and broad scope of this reaction. These experiments demonstrate the ability of the λ3-azidoiodane reagent to undergo I-N bond homolysis under mild conditions to form λ2-iodanyl and azidyl radicals that undergo highly site-selective and rate-limiting abstraction of a hydrogen atom from the substrate. The resultant alkyl radical then combines rapidly with a resting state iron(III)-azide complex, which is generated by the reaction of the λ3-azidoiodane with the iron(II)(pybox) complex, to form the C(sp3)-N3bond. This mechanism is supported by the independent synthesis of well-defined iron complexes characterized by cyclic voltammetry, X-ray diffraction, and EPR spectroscopy, and by the reaction of the iron complexes with alkanes and the λ3-azidoiodane. Reaction monitoring and kinetic studies further reveal an unusual effect of the catalyst on the rate of formation of product and consumption of reactants and suggest a blueprint for the development of new processes leading to late-stage functionalization of C(sp3)-H bonds.

Alcohol Etherification via Alkoxy Radicals Generated by Visible-Light Photoredox Catalysis

A mechanistically divergent method is described that, employing a commercially available hypervalent iodine(III) reagent, generates alkoxy radicals from 1°, 2°, and 3° alcohols and allows their use in the functionalization of C(sp3)-H and C(sp2)-H bonds. This visible-light photoredox catalysis produces alkyl ethers via 1,5/6-hydrogen atom transfer or aryl ethers via 1,5-addition. This mild methodology provides a practical strategy for the synthesis of acetals, orthoesters, tetrahydrofurans, and chromanes.

LASER RAMAN INVESTIGATION OF SOLID STATE REARRANGEMENT OF BIS(O-IODOBENZOYL) PEROXIDE INTO 1-(2-IODOBENZOYLOXY)-1, 2-BENZIODOXOLIN-3-ONE.

In solid state, the thermal rearrangement of bis(O-iodobenzoyl) peroxide which yields 1-(2 prime -iodobenzoyloxy)-1,2-benziodoxolin-3-one, is investigated by laser Raman spectroscopy. The intramolecular vibration spectra are used to characterize this chemical rearangement. The phonon spectra obtained as a function of the rearrangement progress show that, in spite of the reported topotactic nature of the reaction, it proceeds by a heterogeneous mechanism. A temperature dependence study of the phonon spectra reveal no mode-softening for any optical phonons. Therefore, no evidence has been found for this reaction to be phonon-assisted.