On the induced oxidation of iodobenzene during the oxidation of acetaldehyde in an atmosphere of oxygen

Jorissen, W. P.; Dekking, A. C. B.

doi:10.1002/recl.19380571010

Cited by 5 publications

(2 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As we considered strategies to marry O 2 reduction with aryl iodide oxidation, we were attracted to the potential to intercept oxidizing intermediates generated during aldehyde autoxidation. Aldehyde autoxidation proceeds via a radical chain mechanism to generate peracid intermediates, which subsequently engage in Baeyer–Villiger chemistry to afford carboxylic acids (Figure a). , Inspired by reports of oxygen-atom transfer from reactive autoxidation intermediates (Figure b), − we envisioned that aerobic synthesis of hypervalent iodine compounds could be achieved by intercepting aerobically generated peracid intermediates with aryl iodides (Figure c) …”

Section: Aerobic Hypervalent Iodine Chemistry and Catalysismentioning

confidence: 99%

“… 39 , 40 Inspired by reports of oxygen-atom transfer from reactive autoxidation intermediates ( Figure 2 b), 41 − 44 we envisioned that aerobic synthesis of hypervalent iodine compounds could be achieved by intercepting aerobically generated peracid intermediates with aryl iodides ( Figure 2 c). 45 …”

Section: Aerobic Hypervalent Iodine Chemistry and Catalysismentioning

confidence: 99%

See 1 more Smart Citation

Iodanyl Radical Catalysis

2023

View full text Add to dashboard Cite

Conspectus Hypervalent iodine reagents find application as selective chemical oxidants in a diverse array of oxidative transformations. The utility of these reagents is often ascribed to (1) the proclivity to engage being selective two-electron redox transformations; (2) facile ligand exchange at the three-centered, four-electron (3c–4e) hypervalent iodine–ligand (I–X) bonds; and (3) the hypernucleofugacity of aryl iodides. One-electron redox and iodine radical chemistry is well-precedented in the context of inorganic hypervalent iodine chemistryfor example, in the iodide–triiodide couple that drives dye-sensitized solar cells. In contrast, organic hypervalent iodine chemistry has historically been dominated by the two-electron I(I)/I(III) and I(III)/I(V) redox couples, which results from intrinsic instability of the intervening odd-electron species. Transient iodanyl radicals (i.e., formally I(II) species), generated by reductive activation of hypervalent I–X bonds, have recently gained attention as potential intermediates in hypervalent iodine chemistry. Importantly, these open-shell intermediates are typically generated by activation of stoichiometric hypervalent iodine reagents, and the role of the iodanyl radical in substrate functionalization and catalysis is largely unknown. Our group has been interested in advancing the chemistry of iodanyl radicals as intermediates in the sustainable synthesis of hypervalent I(III) and I(V) compounds and as novel platforms for substrate activation at open-shell main-group intermediates. In 2018, we disclosed the first example of aerobic hypervalent iodine catalysis by intercepting reactive intermediates in aldehyde autoxidation chemistry. While we initially hypothesized that the observed oxidation was accomplished by aerobically generated peracids via a two-electron I(I)-to-I(III) oxidation reaction, detailed mechanistic studies revealed the critical role of acetate-stabilized iodanyl radical intermediates. We subsequently leveraged these mechanistic insights to develop hypervalent iodine electrocatalysis. Our studies resulted in the identification of new catalyst design principles that give rise to highly efficient organoiodide electrocatalysts that operate at modest applied potentials. These advances addressed classical challenges in hypervalent iodine electrocatalysis related to the need for high applied potentials and high catalyst loadings. In some cases, we were able to isolate the anodically generated iodanyl radical intermediates, which allowed direct interrogation of the elementary chemical reactions characteristic of iodanyl radicals. Both substrate activation via bidirectional proton-coupled electron transfer (PCET) reactions at I(II) intermediates and disproportionation reactions of I(II) species to generate I(III) compounds have been experimentally validated. This Account discusses the emerging synthetic and catalytic chemistry of iodanyl radicals. Results from our group have demonstrated that these open-shell species can play a critical role in...

show abstract

Section: Aerobic Hypervalent Iodine Chemistry and Catalysismentioning

confidence: 99%

Section: Aerobic Hypervalent Iodine Chemistry and Catalysismentioning

confidence: 99%

Iodanyl Radical Catalysis

2023

View full text Add to dashboard Cite

show abstract

Sustainable Methods in Hypervalent Iodine Chemistry

Frey

Maity

Tan

et al. 2022

Iodine Catalysis in Organic Synthesis

View full text Add to dashboard Cite

Oxidation Catalysis by an Aerobically Generated Dess–Martin Periodinane Analogue

et al. 2018

View full text Add to dashboard Cite

Hypervalent iodine(V) reagents,s uch as Dess-Martin periodinane (DMP) and 2-iodoxybenzoic acid (IBX), are broadly useful oxidants in chemical synthesis.D evelopment of strategies to generate these reagents from dioxygen (O 2 )would immediately enable use of O 2 as aterminal oxidant in ab road arrayo fs ubstrate oxidation reactions.R ecently we disclosed the aerobic synthesis of I(III) reagents by intercepting reactive oxidants generated during aldehyde autoxidation. In this work, aerobic oxidation of iodobenzenes is coupled with disproportionation of the initially generated I(III) compounds to generate I(V) reagents.T he aerobically generated I(V) reagents exhibit substrate oxidation chemistry analogous to that of DMP.T he developed aerobic generation of I(V) has enabled the first application of I(V) intermediates in aerobic oxidation catalysis.

show abstract

On the induced oxidation of iodobenzene during the oxidation of acetaldehyde in an atmosphere of oxygen

Cited by 5 publications

References 2 publications

Iodanyl Radical Catalysis

Iodanyl Radical Catalysis

Sustainable Methods in Hypervalent Iodine Chemistry

Oxidation Catalysis by an Aerobically Generated Dess–Martin Periodinane Analogue

Contact Info

Product

Resources

About