Aminals as powerful XAT-reagents: activation of fluorinated alkyl chlorides

Kostromitin, Vladislav S.; Sorokin, Artem O.; Levin, Vitalij V.; Dilman, Alexander D.

doi:10.1039/d3sc00027c

Cited by 20 publications

(16 citation statements)

References 43 publications

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“…Strategies for polyfluoroalkylation of organic scaffolds using α‐aminoalkyl radical mediated XAT was further extended by the Sureshkumar group (Scheme 17). [33] By employing vinyl cyclopropanes 82 as the electrophilic centre and polyfluoro bromoalkanes 83 as the nucleophilic centre, a cascade difluoroalkylative ring‐opening pathway was achieved which bypasses the requirement of a HAT agent as mentioned in the prior reports, and affords allylic difluoroalkyl products 84 [31,32] …”

Section: C(sp3)–c(sp3) Bond Formationmentioning

confidence: 95%

“…In the beginning of 2023, the Dilman group showcased a similar system that uses polyfluorinated chloroalkanes as starting materials 74 (Scheme 16). [32] Formation of a unique α‐aminoalkyl radical 76 from aminal triazinane N1 and subsequent XAT with 74 forms alkyl radical intermediate 77 . This reactive species 77 attacks olefin 72 and subsequently undergoes HAT with alkyl thiol 79 thereby forming the desired product 75 .…”

Section: C(sp3)–c(sp3) Bond Formationmentioning

confidence: 99%

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An Overview of α‐Aminoalkyl Radical Mediated Halogen‐Atom Transfer

2023

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The merging of photocatalysis with halogen‐atom transfer (XAT) processes has proven to be a versatile tool for the generation of carbon‐centered radicals in organic synthesis. XAT processes are unique in that they generate radicals without requiring the use of strong reductants necessary for the traditional single electron transfer (SET) activation of halides. Pathways to achieve XAT in synthetic applications can be categorized into three major sections: i) heteroatom‐based activators, ii) metal‐based activators, and iii) carbon‐based activators among which α‐aminoalkyl radicals have taken the center stage. Access to these α‐aminoalkyl radicals as XAT reagents has gained significant attention in the past few years due to the robustness of the reactions, the simplicity of the reagents required, and the broadness of their applications. Generation of these α‐aminoalkyl radicals is simply achieved through the single electron oxidation of tertiary amines, which after deprotonation at the α‐position generates the α‐aminoalkyl radicals. Due to the wide scope of tertiary amines available and the tunable nucleophilicity of α‐aminoalkyl radical formed, this strategy has become an attractive alternative to heteroatom/metal‐based radicals for XAT. In this minireview, we focus our attention on recent (2020‐2023) developments and uses of this robust technology to mediate XAT processes.

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Section: C(sp3)–c(sp3) Bond Formationmentioning

confidence: 95%

Section: C(sp3)–c(sp3) Bond Formationmentioning

confidence: 99%

An Overview of α‐Aminoalkyl Radical Mediated Halogen‐Atom Transfer

2023

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“…Very recently, Dilman and co-workers 42 utilized 1,3,5-trimethyl-1,3,5-triazinane ( 17.4 ) as a novel XAT reagent, which can activate the C–Cl bond of fluorinated alkyl chlorides under visible light irradiation (Scheme 17). The protocol features wide substrate scope and mild conditions.…”

Section: Chlorine Atom Transfer (Cat) Strategymentioning

confidence: 99%

Photoinduced activation of alkyl chlorides

Zhai

Fang

et al. 2023

Chem. Soc. Rev.

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“…This method is applicable to a variety of unactivated alkenes, including pharmaceutical compounds, natural products, and derivatives for efficient hydrodifluoromethylation. Recently, another elegant photoinduced radical hydrofluoroalkylation of unactivated alkenes with fluorinated alkyl chlorides was established by Dilman's group, using readily available 1,3,5‐trimethyl‐1,3,5‐triazinane as an efficient reagent for halogen atom transfer (Scheme 16b) [29b] …”

Section: C−h Functionalization Reactionsmentioning

confidence: 99%

Thiols as Powerful Atom Transfer Catalyst: Opportunities in Photoredox‐Mediated Reactions

Bao

Wang

2023

Adv Synth Catal

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The employing visible light to drive organic transformations is the most promising choice to meet the needs for green synthesis, in which the reactions promoted by visible light may provide a more efficient and greener method. Currently, the most abundant methods for activation and functionalization of reaction substrates have relied on the direct single‐electron transfer (SET) between the excited photocatalyst and substrates, and these wonderful works were summarized and docoumented in many reviews. As a complement to the above reactions, the photoredox‐mediated atom transfer transformations (photocatalyst‐to‐HAT catalyst‐to‐substrates) to generate radical species are showing an explosively growing trend. In this review, we highlight recent significant developments in this rapidly growing area, mainly focusing on the photoinduced base‐to‐substrates charge transfer reactions.

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Aminals as powerful XAT-reagents: activation of fluorinated alkyl chlorides

Abstract: Readily available 1,3,5-trimethyl-1,3,5-triazinane serves as an efficient reagent for the halogen atom transfer. Under photocatalytic conditions, the triazinane generates α-aminoalkyl radical, which can activate the C-Cl bond of fluorinated alkyl...

Cited by 20 publications

References 43 publications

An Overview of α‐Aminoalkyl Radical Mediated Halogen‐Atom Transfer

An Overview of α‐Aminoalkyl Radical Mediated Halogen‐Atom Transfer

Photoinduced activation of alkyl chlorides

Thiols as Powerful Atom Transfer Catalyst: Opportunities in Photoredox‐Mediated Reactions

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