Radical‐Chain Hydrosilylation of Alkenes Enabled by Triplet Energy Transfer DOI

Shixun Guo,

Wei Wang, Yongqiang Zhang

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 9, 2024

Abstract Development of mild, robust and metal‐free catalytic approach for the hydrosilylation alkenes is critical to advancement modern organosilicon chemistry given their powerful capacity in construction various C−Si bonds. Herein, we wish disclose a visible light‐triggered organophotocatalytic strategy, which proceeds via triplet energy transfer ( EnT )‐enabled radical chain pathway. Notably, this redox‐neutral protocol capable accommodating broad spectrum electron‐deficient ‐rich with excellent functional group compatibility. Electron‐deficient are more reactive reaction could be finished within couple minutes even PBS solution extremely low concentration, suggests its click‐like potential organic synthesis. The preparative power transformations has been further highlighted number complex settings, including late‐stage functionalization scale‐up experiments. Furthermore, although only highly (TMS) 3 SiH suitable hydrosilane substrate, our studies revealed great reactivity versatility Si− diverse Si−Si bond cleavage‐based transformations, enabling rapid introduction groups facile valuable quaternary silicon architectures.

Language: Английский

Deacylative Homolysis of Ketone C(sp3)–C(sp2) Bonds: Streamlining Natural Product Transformations DOI
Michal Šimek, Sujit Mahato,

Brady W. Dehnert

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

The homolytic cleavage of C–C bonds adjacent to specific functional groups has lately emerged as a versatile approach for molecular diversification. Despite the ubiquity and synthetic utility ketones, radical fragmentation their α-C–C proven be formidable challenge. Here, we present broadly applicable deacylative strategy designed homolytically cleave aliphatic ketones various complexities, including transformations cycloalkanones into carboxylic acids tethered C-centered free radicals that can engaged in diverse radical-based processes. method involves ketone activation through treatment with hydrogen peroxide, yielding gem-dihydroperoxides. Subsequent single-electron-transfer reduction mediated by low-valent metal complex generates alkyl captured selectively radicophile choice, catalytic cross-coupling. logic our functionalization is exemplified total synthesis 14 natural products, one analogue, two drugs starting from readily available showcasing its transformative power settings. This obviates need reagents allows controlled conversion reconstructed making process highly across spectrum domains.

Language: Английский

Citations

1
Modular reductive radical-polar crossover-based acyl migration reactions of N-vinylimides with alkyl, silyl, and acyl radicals DOI Creative Commons

Yutao Jing,

Li Zhang,

Li Qiu

et al.

RSC Advances, Journal Year: 2025, Volume and Issue: 15(15), P. 11582 - 11586

Published: Jan. 1, 2025

Generation of α-amino ketones: photocatalytic radical addition/acyl migration cascade processes were reported on reactions enamides with dihydroquinazolinones or acyl oxime acetates.

Language: Английский

Citations

0
Organo-Photoredox Catalyzed gem-Difluoroallylation of Ketone-Derived Dihydroquinazolinones with α-Trifluoromethyl Alkenes via C(sp3)-C Bond and C(sp3)-F Bond Cleavage DOI
Yue Zhang,

Tianshuai Zhu,

Yuqian Lin

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(27), P. 5561 - 5568

Published: Jan. 1, 2024

An organo-photoredox catalyzed defluorinative alkylation of ketone-derived dihydroquinazolinones with α-trifluoromethyl alkenes is described, providing a facile access to diverse set gem -difluoroalkenes.

Language: Английский

Citations

3
Ketone-Derived Pro-aromatic Reagents for Radical Group Transfer Reactions and Deconstructive Functionalizations DOI
Ivy L. Librando, Hsuan‐Hung Liao, Shinje Miñoza

et al.

Synlett, Journal Year: 2023, Volume and Issue: 35(10), P. 1072 - 1088

Published: Oct. 24, 2023

Abstract The recent prominence of ketones as handles for sp3-rich radicals has expanded the paradigm synthetic utility ketones, putting ubiquitous functional group once again into spotlight in years. One emerging strategy arose through ketone-derived pro-aromatic reagents form dihydrobenzothiazoline (BTZ), dihydroquinazolinone (DHQZ), dihydropyrazole (DHP), and dihydro-1,2,4-triazole (DHT) key intermediates aromaticity-promoted C–C bond homolytic fission. formed sp3-radicals could then participate various radical functionalizations, including alkylations, arylations, olefination, alkynylation, silylations, amination, thiolation, deuteration, among others, either photocatalytic, thermal, or oxidative conditions. In this review, we highlight implications advances using these transfer reactions deconstructive functionalization. 1 Introduction 2 Aromatization-Driven Bond Scission Ketones 3 Photochemical Reactions Ketone-Derived Pro-aromatic Reagents 4 Non-photochemical 5 Conclusion Future Outlook

Language: Английский

Citations

5
Photoredox catalyzed release of carbon-based radicals from 2-substituted-1,3-imidazolidines DOI Creative Commons
Adrián Luguera Ruiz,

Elena Mariani,

Stefano Protti

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(3), P. 661 - 667

Published: Dec. 7, 2023

We describe herein easily oxidizable 2-substituted-1,3-imidazolidines for the photocatalyzed generation of (substituted) alkyl radicals forging C(sp 3 )–C(sp ) bonds under metal-free conditions.

Language: Английский

Citations

2
Pro‐aromatic Dihydroquinazolinones – From Multigram Synthesis to Reagents for Gram‐scale Metallaphotoredox Reactions DOI

Zong‐Nan Tsai,

Liyun Li,

Aira Shayne Paculba

et al.

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 19(3)

Published: Dec. 16, 2023

Abstract Dihydroquinazolinone (DHQZ) has recently been harnessed as a ketone‐derived pro‐aromatic reagent extensively employed in (metalla)photoredox reactions versatile group transfer agents. In this work, we outline column chromatography‐free protocol for the multigram‐scale synthesis of DHQZs well its use gram‐scale nickel/photoredox dual‐catalyzed cross‐coupling single‐batch, photoflow, and simultaneous multiple smaller batches. While single‐batch approach leveraged moderate yields, simple plug‐flow photoreactor also exhibited amenable productivity (up to 45 % yield) despite heterogeneous base. Meanwhile, performing metallaphotoredox‐catalyzed reaction batches an improvised facilitated high yields up 59 good reproducibility, implying convenient alternative absence photoflow setups.

Language: Английский

Citations

2
Radical‐Chain Hydrosilylation of Alkenes Enabled by Triplet Energy Transfer DOI

Shixun Guo,

Wei Wang, Yongqiang Zhang

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 9, 2024

Abstract Development of mild, robust and metal‐free catalytic approach for the hydrosilylation alkenes is critical to advancement modern organosilicon chemistry given their powerful capacity in construction various C−Si bonds. Herein, we wish disclose a visible light‐triggered organophotocatalytic strategy, which proceeds via triplet energy transfer ( EnT )‐enabled radical chain pathway. Notably, this redox‐neutral protocol capable accommodating broad spectrum electron‐deficient ‐rich with excellent functional group compatibility. Electron‐deficient are more reactive reaction could be finished within couple minutes even PBS solution extremely low concentration, suggests its click‐like potential organic synthesis. The preparative power transformations has been further highlighted number complex settings, including late‐stage functionalization scale‐up experiments. Furthermore, although only highly (TMS) 3 SiH suitable hydrosilane substrate, our studies revealed great reactivity versatility Si− diverse Si−Si bond cleavage‐based transformations, enabling rapid introduction groups facile valuable quaternary silicon architectures.

Language: Английский

Citations

0