The Chemical Record, Год журнала: 2023, Номер 23(11)
Опубликована: Июнь 26, 2023
Abstract Due to their high versatility borylated and silylated compounds are inevitable synthons for organic chemists. To escape the classical hydroboration/hydrosilylation paradigm, chemists turned attention more modern green methods such as photoredox chemistry electrosynthesis. This account focuses on novel generation of boryl silyl radicals forge C−B C−Si bonds from our group.
Язык: Английский
Organic Letters, Год журнала: 2024, Номер 26(5), С. 1011 - 1016
Опубликована: Янв. 30, 2024
A novel strategy was developed to generate silyl radicals from silylboronic pinacol esters (SPEs) through nucleohomolytic substitution of boron with aminyl radicals. We successfully applied this obtain diverse organosilicon compounds using SPEs and N-nitrosamines under photoirradiation without any catalyst. The ability access offers a new perspective for chemists rapidly construct Si–X bonds.
Язык: Английский
Процитировано
11
Chemistry - A European Journal, Год журнала: 2024, Номер 30(41)
Опубликована: Май 8, 2024
Abstract We have established a facile and efficient protocol for the generation of germyl radicals by employing photo‐excited electron transfer (ET) in an donor‐acceptor (EDA) complex to drive hydrogen‐atom (HAT) from hydride (R 3 GeH). Using catalytic amount EDA commercially available thiol benzophenone derivatives, ET‐HAT cycle smoothly proceeds simply upon blue‐light irradiation without any transition metal or photocatalyst. This also affords silyl radical hydride.
Язык: Английский
Процитировано
4
ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 2150 - 2157
Опубликована: Янв. 22, 2025
This study reports the development of a photocatalytic germanyl functionalization unactivated olefins. A modular approach to alkylgermanium trihalides was realized through three-component radical reaction involving fluoroalkyl bromides and commercially available GeBr2 in redox-neutral process. The target organogermanes were readily obtained via one-pot derivatization using various Grignard reagents, demonstrating good functional group compatibility with amides, esters ketones. work highlights utility Ge(II) reagents constructing C–Ge bonds photoredox catalysis. Notably, selectivity capturing electrophilic or nucleophilic radicals by found be significantly influenced halide ligands on GeX2.
Язык: Английский
Процитировано
0
Chemical Communications, Год журнала: 2024, Номер 60(35), С. 4633 - 4647
Опубликована: Янв. 1, 2024
This review briefly summarizes the utilization of allylsilane in photoredox catalysis. It highlights underlying mechanisms for formation C–C/C–heteroatom bond with various functionalities mild conditions high selectivity.
Язык: Английский
Процитировано
3
Chemistry - A European Journal, Год журнала: 2023, Номер 29(45)
Опубликована: Июнь 3, 2023
The hydrosilylation of alkenes is one the most important methods for synthesis organosilicon compounds. In addition to platinum-catalyzed hydrosilylation, silyl radical reactions are notable as economic reactions. An efficient and widely applicable reaction was developed by using 2-silylated dihydroquinazolinone derivatives under photocatalytic conditions. Electron-deficient styrene underwent give products in good high yields. Mechanistic studies indicated that photocatalyst functioned not a photoredox catalyst but an energy transfer catalyst. DFT calculations clarified triplet excited state released through homolytic cleavage carbon-silicon bond, this followed hydrogen atom pathway, redox pathway.
Язык: Английский
Процитировано
7
The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(21), С. 15623 - 15629
Опубликована: Окт. 9, 2024
We have developed a visible-light-induced method to photolyze digermanes through single-electron oxidation using photocatalyst, in contrast direct excitation, generate germyl radicals and achieve the hydro/deuteriogermylation of alkenes. This protocol allows previously elusive incorporation small trimethylgermyl group deuterium, metabolically stable bioisosteres tert-butyl hydrogen, respectively, making this approach attractive not only organic synthesis but also medicinal chemistry.
Язык: Английский
Процитировано
1
Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(22), С. 4618 - 4633
Опубликована: Окт. 16, 2024
Abstract Germanium (Ge), a congener of carbon, possesses unique properties that hold extensive potential for applications across multiple domains. Recent years have seen significant progress in the development carbon‐germanium bond formation strategies, particularly those more challenging C( sp 3 )−Ge bonds. This review systematically summarizes recent advances forming methodologies, with particular emphasis on (1) versatility transition‐metals, including iron, nickel, copper, rhodium and palladium, as catalysts broadening reaction scope controlling selectivity; (2) powerfulness organic photocatalysis achieving mild selective formation, (3) sustainability catalytic electrosynthesis facilitating chemical oxidant‐/reductant‐ free conversions. Additionally, examples (4) non‐catalytic strategies are also discussed. The representative scopes, well mechanistic proposals, these protocols highlighted. Through an overview current state research, this aims to offer insights into construction bonds, provide perspectives future research directions address challenges.
Язык: Английский
Процитировано
1
The Chemical Record, Год журнала: 2023, Номер 23(11)
Опубликована: Июнь 26, 2023
Abstract Due to their high versatility borylated and silylated compounds are inevitable synthons for organic chemists. To escape the classical hydroboration/hydrosilylation paradigm, chemists turned attention more modern green methods such as photoredox chemistry electrosynthesis. This account focuses on novel generation of boryl silyl radicals forge C−B C−Si bonds from our group.
Язык: Английский
Процитировано
3