The Direct C–H Difluoromethylation of Heteroarenes Based on the Photolysis of Hypervalent Iodine(III) Reagents That Contain Difluoroacetoxy Ligands

Sakamoto, Ryu; Kashiwagi, Hirotaka; Maruoka, Keiji

doi:10.1021/acs.orglett.7b02416

Cited by 124 publications

(84 citation statements)

References 62 publications

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“…Maruoka et al. recently reported the difluoromethylation of heteroaromatic compounds using hypervalent iodine I (Figure a) under irradiation with violet light (400 nm) . Wang et al.…”

Section: Introductionmentioning

confidence: 99%

A Direct S₀→T_n Transition in the Photoreaction of Heavy‐Atom‐Containing Molecules

et al. 2020

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According to the Grotthuss–Draper law, light must be absorbed by a substrate to initiate a photoreaction. There have been several reports, however, on the promotion of photoreactions using hypervalent iodine during irradiation with light from a non‐absorbing region. This contradiction gave rise to a mystery regarding photoreactions involving hypervalent iodine. We demonstrated that the photoactivation of hypervalent iodine with light from the apparently non‐absorbing region proceeds via a direct S0→Tn transition, which has been considered a forbidden process. Spectroscopic, computational, and synthetic experimental results support this conclusion. Moreover, the photoactivation mode could be extended to monovalent iodine and bromine, as well as bismuth(III)‐containing molecules, providing new possibilities for studying photoreactions that involve heavy‐atom‐containing molecules.

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“…Maruoka et al. recently reported the difluoromethylation of heteroaromatic compounds using hypervalent iodine I (Figure a) under irradiation with violet light (400 nm) . Wang et al.…”

Section: Introductionmentioning

confidence: 99%

A Direct S₀→T_n Transition in the Photoreaction of Heavy‐Atom‐Containing Molecules

et al. 2020

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“…[10] We were encouraged by studies demonstrating that the photolysis of preformed hypervalent iodine(III) reagents enables direct C À Hd ifluoromethylation of heteroarenes. [11] Hypervalent iodine(III) reagents are also suitable for the hydroaryldifluoromethylation of alkenes under iridium-based photoredox catalysis. [12] These observations led us to consider that visible-light irradiation could enable hydrodifluoromethylation of alkenes in the absence of ap hotocatalyst using inexpensive difluoroacetic acid and the oxidant phenyliodine(III) diacetate (PIDA) in as olvent capable of hydrogen atom transfer, such as tetrahydrofuran (THF).…”

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Hydrodifluoromethylation of Alkenes with Difluoroacetic Acid

Meyer

Hell

Misale³

et al. 2019

Angew Chem Int Ed

128

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Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.Scheme 3. Scaled-up synthesis of building blocks that are highly valuable for medicinal chemistry.Scheme 4. Mechanistic considerations. Yields were determined by 19 FNMR spectroscopy using trifluorotoluene as internalstandard. Yields of isolated products are shown in parentheses. dr = diastereomeric ratio, nd = not detected.

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“…Our objective was to develop an operationally simple and scalable process for the hydrodifluoromethylation of alkenes using inexpensive difluoroacetic acid under visible‐light activation . We were encouraged by studies demonstrating that the photolysis of preformed hypervalent iodine(III) reagents enables direct C−H difluoromethylation of heteroarenes . Hypervalent iodine(III) reagents are also suitable for the hydroaryldifluoromethylation of alkenes under iridium‐based photoredox catalysis .…”

Section: Methodsmentioning

confidence: 99%

Hydrodifluoromethylation of Alkenes with Difluoroacetic Acid

Meyer

Hell

Misale³

et al. 2019

Angewandte Chemie

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A facile method for the regioselective hydrodifluoromethylation of alkenes is reported using difluoroacetic acid and phenyliodine(III) diacetate in tetrahydrofuran under visible‐light activation. This metal‐free approach stands out as it uses inexpensive reagents, does not require a photocatalyst, and displays broad functional group tolerance. The procedure is also operationally simple and scalable, and provides access in one step to high‐value building blocks for application in medicinal chemistry.

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The Direct C–H Difluoromethylation of Heteroarenes Based on the Photolysis of Hypervalent Iodine(III) Reagents That Contain Difluoroacetoxy Ligands

Cited by 124 publications

References 62 publications

A Direct S₀→T_n Transition in the Photoreaction of Heavy‐Atom‐Containing Molecules

A Direct S₀→T_n Transition in the Photoreaction of Heavy‐Atom‐Containing Molecules

Hydrodifluoromethylation of Alkenes with Difluoroacetic Acid

Hydrodifluoromethylation of Alkenes with Difluoroacetic Acid

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The Direct C–H Difluoromethylation of Heteroarenes Based on the Photolysis of Hypervalent Iodine(III) Reagents That Contain Difluoroacetoxy Ligands

Cited by 124 publications

References 62 publications

A Direct S0→Tn Transition in the Photoreaction of Heavy‐Atom‐Containing Molecules

A Direct S0→Tn Transition in the Photoreaction of Heavy‐Atom‐Containing Molecules

Hydrodifluoromethylation of Alkenes with Difluoroacetic Acid

Hydrodifluoromethylation of Alkenes with Difluoroacetic Acid

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A Direct S₀→T_n Transition in the Photoreaction of Heavy‐Atom‐Containing Molecules

A Direct S₀→T_n Transition in the Photoreaction of Heavy‐Atom‐Containing Molecules