General Defluoroalkylation of Trifluoromethylarenes with Both Electron-Donating and -Withdrawing Alkenes DOI
Mengqi Zhu, Qiaolin Wang, Huawen Huang

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(17), С. 12591 - 12609

Опубликована: Авг. 14, 2024

The incorporation of gem-difluoromethylene units into organic molecules remains a formidable challenge. Conventional methodologies for constructing aryldifluoromethyl derivatives relied on the use high-functional fluorinating regents under harsh conditions. Herein, we report general and efficient photoredox catalytic systems defluoroalkylation readily available trifluoromethylarenes through selective C–F cleavage to deliver gem-difluoromethyl radicals which proceed reductive addition both electron-donating withdrawing alkenes transition-metal free Mechanistic studies reveal that thiol serves as photocatalyst HAT reagent visible light irradiation. This synergistic photocatalysis catalysis protocol exhibits ample salient features such high chemo- regioselectivity, broad substrate scope, amenable gram-scale synthesis late-stage modification bioactive molecules.

Язык: Английский

Access to germasiloxanes and alkynylgermanes mediated by earth-abundant species DOI Creative Commons
Hanna Stachowiak, Krzysztof Kuciński, Konstancja Broniarz

и другие.

Scientific Reports, Год журнала: 2023, Номер 13(1)

Опубликована: Апрель 6, 2023

The reactions between silanols or terminal acetylenes with alkynylgermanes have been accomplished using potassium bis(trimethylsilyl)amide as the catalyst. This strategy has provided an entry point into various organogermanes including germasiloxanes and alkynylgermanes. Remarkably, not only KHMDS but also simple bases such KOH can serve efficient catalysts in this process.

Язык: Английский

Процитировано

9
A general photocatalytic hydrodefluorination and defluoroalkylation of electronically-variable ArCF3 by changing commercially-available arenethiolates DOI

Yuanyang Jiang,

Chenxiu Han,

Zipeng Guo

и другие.

Green Chemistry, Год журнала: 2024, Номер 26(8), С. 4518 - 4527

Опубликована: Янв. 1, 2024

The selection of electronically-different thiolate-based photosensitizers is employed to achieve a precise and specific C–F bond defluorination broad range trifluoromethylarenes, enabling the synthesis 88 α,α-difluoromethyl compounds.

Язык: Английский

Процитировано

3
Photoinduced Remote Selective C(sp3)−H Alkylation Mediated by Cesium Formate DOI

Vijay Kumar Simhadri,

Rupam Sur,

Veera Reddy Yatham

и другие.

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(32)

Опубликована: Май 13, 2024

Abstract Herein, we developed a photoinduced remote selective C( sp 3 )−H alkylation of protected amines in the presence cesium formate. The were synthesized from commercially available inexpensive 2‐iodo benzoyl chloride. Under mild reaction conditions, situ generated aryl radical is converted to α‐amidoalkyl via [1,5]‐HAT process, which combines with different Michael acceptors and affords corresponding products good yields. Preliminary mechanistic studies revealed that formate anion acts as source carbon dioxide (CO 2 ⋅ − ) hydrogen atom donor was directly confirmed by isotope‐labeling studies.

Язык: Английский

Процитировано

3
Defluorinative Functionalization Approach led by Difluoromethyl Anion Chemistry DOI Creative Commons
Kensuke Muta, Kazuhiro Okamoto, Hiroki Nakayama

и другие.

Опубликована: Май 14, 2024

Organofluorine compounds have greatly benefited the pharmaceutical, agrochemical, and materials sectors. However, they are plagued by concerns associated with PFAS. Additionally, widespread use of trifluoromethyl group is facing imminent regulatory scrutiny. Defluorinative functionalization, which converts to difluoromethyl motifs, represents most efficient synthetic strategy. general methods for robust C(sp3)–F bond transformations remain elusive due challenges in selectivity functional tolerance. Here, we present a method defluorinative functionalization via anion flow. This new approach tames reactive anion, enabling diverse transformations. Our methodology offers versatile platform drug agrochemical discovery, overcoming limitations fluorinated motifs.

Язык: Английский

Процитировано

2
General Defluoroalkylation of Trifluoromethylarenes with Both Electron-Donating and -Withdrawing Alkenes DOI
Mengqi Zhu, Qiaolin Wang, Huawen Huang

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(17), С. 12591 - 12609

Опубликована: Авг. 14, 2024

The incorporation of gem-difluoromethylene units into organic molecules remains a formidable challenge. Conventional methodologies for constructing aryldifluoromethyl derivatives relied on the use high-functional fluorinating regents under harsh conditions. Herein, we report general and efficient photoredox catalytic systems defluoroalkylation readily available trifluoromethylarenes through selective C–F cleavage to deliver gem-difluoromethyl radicals which proceed reductive addition both electron-donating withdrawing alkenes transition-metal free Mechanistic studies reveal that thiol serves as photocatalyst HAT reagent visible light irradiation. This synergistic photocatalysis catalysis protocol exhibits ample salient features such high chemo- regioselectivity, broad substrate scope, amenable gram-scale synthesis late-stage modification bioactive molecules.

Язык: Английский

Процитировано

2