Metathetical Redox Reaction of (Diacetoxyiodo)arenes and Iodoarenes

Lauriers, Antoine Jobin-Des; Legault, Claude Y.

doi:10.3390/molecules201219874

Cited by 21 publications

(9 citation statements)

References 39 publications

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“…The Rh catalyst acts thus as a Lewis acid to facilitate the Int6 → Int7 process. A similar role of Lewis acid catalysts has been reported in previous studies by us and others, ,,− involving isomerization of hypervalent iodine compounds with the assistance of, for example, BF 3 , Zn, and Ag ions, facilitating the further reactions.…”

Section: Resultssupporting

confidence: 75%

Mechanisms of Rh-Catalyzed Oxyfluorination and Oxytrifluoromethylation of Diazocarbonyl Compounds with Hypervalent Fluoroiodine

2018

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The reaction mechanisms of rhodium-catalyzed geminal oxyfluorination and oxytrifluoromethylation of diazocarbonyl compounds with fluoro-benziodoxole and Togni reagents are investigated by means of density functional theory calculations. It is shown that the two reactions follow very similar mechanisms, involving N 2 dissociation to form a Rh− carbene intermediate, alcohol insertion and proton transfer resulting in a stable Rh−enol intermediate, and concerted proton transfer/electrophilic addition of the hypervalent iodine reagent to the enol. Isomerization of the hypervalent iodine takes then place before a ligand coupling affords the final product. The role of the dirhodium catalyst in facilitating the various steps of the reaction is discussed. The presented mechanisms are consistent with available experimental information, and the obtained insights allow for extension to other reactions involving hypervalent iodine reagents.

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Section: Resultssupporting

confidence: 75%

Mechanisms of Rh-Catalyzed Oxyfluorination and Oxytrifluoromethylation of Diazocarbonyl Compounds with Hypervalent Fluoroiodine

2018

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“…Reaction optimization showed the need for an excess of Lewis acid, BF 3 ⋅ OEt 2 , to achieve high yields. This result is consistent with the necessity to form an activated iodonium intermediate to favor ligand exchange with the substrate, as illustrated by our group in a recent experimental/computational study . The Lewis acid could also facilitate imine–enamine tautomerism in the various reaction processes.…”

Section: Enamine and Enamide Substratessupporting

confidence: 90%

Enol and Ynol Surrogates: Promising Substrates for Hypervalent Iodine Chemistry

Lauriers

Legault

2016

Asian J Org Chem

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This reviewisd edicated to Prof. Jean Lessard on the occasion of his 80th birthday Asian Abstract: In numerous iodine(III)-mediated methodologies that involve ketone compounds, the enol tautomer is expected to be the reactive species. In this context,t he exploration of enol and ynol surrogates as substrates is of great interest. Activated p-systems have been shown to exhibit interesting and highly exploitable behavior towardh ypervalent iodine reagents. This has led to the development of nu-merousu seful oxidativet ransformations. Enamines, enamides, enol derivatives, haloalkenes, and haloalkynes are all enol or ynol surrogates that are reactivet owards the most populari odanes and iodonium salts. This Focus Review will describep ast and on-going research involving these substrates to gain insighti nto the similarities and disparities observed in their reactivity profiles.The ORCID identification number(s) for the author(s) of this articlecan be found under http://dx.Scheme4.Proposed mechanism to explain 2 H-arizine formation and acetoxylation.Scheme5.Synthesis of 2-trifluoromethyloxazoles developed by Du, Zhao, and co-workers.Scheme6.Dichlorination of enaminesd evelopedbyZ hao, Du, and co-workers.Scheme7.Optimizedreductive conditionst oconvertthe dihaloimines to their corresponding enamines.

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“…The silver ion acts here as a Lewis acid, facilitating the trans–cis isomerization, a mode of action that has been observed in a number of metal-catalyzed reactions involving hypervalent iodine reagents. 25 − 29 …”

Section: Results and Discussionmentioning

confidence: 99%

“…Then, a trans–cis isomerization of the F 3 CS–I–O bond takes place through TS2 S , with a barrier of 16.7 kcal/mol, yielding Int2 S , which is 9.1 kcal/mol higher in energy than 5·10 . The silver ion acts here as a Lewis acid, facilitating the trans–cis isomerization, a mode of action that has been observed in a number of metal-catalyzed reactions involving hypervalent iodine reagents. − …”

Section: Results and Discussionmentioning

confidence: 99%

Mechanisms of Formation and Rearrangement of Benziodoxole-Based CF₃ and SCF₃ Transfer Reagents

2020

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Togni’s benziodoxole-based reagents are widely used in trifluoromethylation reactions. It has been established that the kinetically stable hypervalent iodine form (I–CF3) of the reagents is thermodynamically less stable than its acyclic ether isomer (O–CF3). On the other hand, the trifluoromethylthio analogue exists in the thermodynamically stable thioperoxide form (O–SCF3), and the hypervalent form (I–SCF3) has been elusive. Despite the importance of these reagents, very little is known about the reaction mechanisms of their syntheses, which has hampered the development of new reagents of the same family. Herein, we use density functional theory calculations to understand the reasons for the divergent behaviors between the CF3 and SCF3 reagents. We demonstrate that they follow different mechanisms of formation and that the metals involved in the syntheses (potassium in the case of the trifluoromethyl reagent and silver in the trifluoromethylthio analogue) play key roles in the mechanisms and greatly influence the possibility of their rearrangements from the hypervalent (I–CF3, I–SCF3) to the corresponding ether-type form (O–CF3, O–SCF3).

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Metathetical Redox Reaction of (Diacetoxyiodo)arenes and Iodoarenes

Cited by 21 publications

References 39 publications

Mechanisms of Rh-Catalyzed Oxyfluorination and Oxytrifluoromethylation of Diazocarbonyl Compounds with Hypervalent Fluoroiodine

Mechanisms of Rh-Catalyzed Oxyfluorination and Oxytrifluoromethylation of Diazocarbonyl Compounds with Hypervalent Fluoroiodine

Enol and Ynol Surrogates: Promising Substrates for Hypervalent Iodine Chemistry

Mechanisms of Formation and Rearrangement of Benziodoxole-Based CF₃ and SCF₃ Transfer Reagents

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Metathetical Redox Reaction of (Diacetoxyiodo)arenes and Iodoarenes

Cited by 21 publications

References 39 publications

Mechanisms of Rh-Catalyzed Oxyfluorination and Oxytrifluoromethylation of Diazocarbonyl Compounds with Hypervalent Fluoroiodine

Mechanisms of Rh-Catalyzed Oxyfluorination and Oxytrifluoromethylation of Diazocarbonyl Compounds with Hypervalent Fluoroiodine

Enol and Ynol Surrogates: Promising Substrates for Hypervalent Iodine Chemistry

Mechanisms of Formation and Rearrangement of Benziodoxole-Based CF3 and SCF3 Transfer Reagents

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Product

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About

Mechanisms of Formation and Rearrangement of Benziodoxole-Based CF₃ and SCF₃ Transfer Reagents