Metal-free, photoinduced remote C(sp3)–H borylation DOI Creative Commons

Jiachen He,

Silas P. Cook

Chemical Science, Journal Year: 2023, Volume and Issue: 14(35), P. 9476 - 9481

Published: Jan. 1, 2023

Described herein is a protocol for the metal-free, photo-induced borylation of unactivated C(sp 3 )–H bonds γ to an O -oxalate hydroxamic ester functionality.

Language: Английский

Terminal C(sp 3 )–H borylation through intermolecular radical sampling DOI
Miao Wang, Yahao Huang, Peng Hu

et al.

Science, Journal Year: 2024, Volume and Issue: 383(6682), P. 537 - 544

Published: Feb. 1, 2024

Hydrogen atom transfer (HAT) processes can overcome the strong bond dissociation energies (BDEs) of inert C(sp

Language: Английский

Citations

34
Photoelectrochemically driven iron-catalysed C(sp3)−H borylation of alkanes DOI

Yangmin Cao,

Cheng Huang, Qingquan Lu

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(4), P. 537 - 544

Published: Jan. 31, 2024

Language: Английский

Citations

23
Catalysis in the Excited State: Bringing Innate Transition Metal Photochemistry into Play DOI Creative Commons
Fabio Juliá

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4665 - 4680

Published: March 5, 2025

Transition metal catalysis is an indispensable tool for organic synthesis that has been harnessed, modulated, and perfected many decades by careful selection of centers ligands, giving rise to synthetic methods with unparalleled efficiency chemoselectivity. Recent developments have demonstrated how light irradiation can also be recruited as a powerful dramatically alter the outcome catalytic reactions, providing access innovative pathways remarkable potential. In this context, adoption photochemical conditions mainstream strategy drive reactions unveiled exciting opportunities exploit rich excited-state framework transition metals applications. This Perspective examines advances in application complexes standalone photocatalysts, exploiting innate reactivity their excited states beyond common use photoredox catalysts. An account relevant examples dissected provide discussion on electronic reorganization, orbitals involved, associated different types states. analysis aims practitioners fundamental principles guiding strategies understand, design, apply light-activation homogeneous synthesis.

Language: Английский

Citations

2
Photoelectrochemical oxidative C(sp3)−H borylation of unactivated hydrocarbons DOI Creative Commons
Ping‐Fu Zhong, Jia‐Lin Tu,

Yating Zhao

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Oct. 16, 2023

Organoboron compounds are of high significance in organic synthesis due to the unique versatility boryl substituents access further modifications. The demand for incorporation moieties into molecular structures has witnessed significant progress, particularly C(sp3)-H borylation hydrocarbons. Taking advantage special characteristics photo/electrochemistry, we herein describe development an oxidative reaction under metal- and oxidant-free conditions, enabled by photoelectrochemical strategy. exhibits broad substrate scope (>57 examples), includes use simple alkanes, halides, silanes, ketones, esters nitriles as viable substrates. Notably, unconventional regioselectivity is achieved, with coupling site selectively located distal methyl group. Our method operationally easily scalable, offers a feasible approach one-step high-value organoboron building blocks from hydrocarbons, which would provide ample opportunities drug discovery.

Language: Английский

Citations

37
The great strides of iron photosensitizers for contemporary organic photoredox catalysis: On our way to the holy grail? DOI
Felix Glaser,

Akin Aydogan,

Benjamin Elias

et al.

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 500, P. 215522 - 215522

Published: Nov. 9, 2023

Language: Английский

Citations

27
Visible-light induced direct C(sp3)–H functionalization: recent advances and future prospects DOI
Jia‐Lin Tu, Yining Zhu, Pengcheng Li

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(18), P. 5278 - 5305

Published: Jan. 1, 2024

This review summarizes the latest methodological advances in photocatalytic C(sp 3 )–H functionalization, with a particular emphasis on formation of C–P, C–B, C–S bonds, etc ., and some prominent efforts asymmetric C–H functionalization.

Language: Английский

Citations

16
2-Aminophenanthroline Ligands Enable Mild, Undirected, Iridium-Catalyzed Borylation of Alkyl C–H Bonds DOI
Isaac Furay Yu, Kyan A. D’Angelo, Ángel D. Hernández-Mejías

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7124 - 7129

Published: March 8, 2024

The catalytic, undirected borylation of alkyl C–H bonds typically occurs at high reaction temperatures or with excess substrate, both, because the low reactivity bonds. Here we report a new iridium system comprising 2-anilino-1,10-phenanthroline as ligand that catalyzes little to no induction period and rates. This superior activation profile 2-aminophenanthroline-ligated catalysts leads broader scope, including reactions sensitive substrates, such epoxides glycosidic acetals, enhanced diastereoselectivity, higher yields borylated products. These also enable alkanes, amines, ethers room temperature for first time. Mechanistic studies imply facile N-borylation under conditions complexes containing N-boryl aminophenanthrolines are competent precatalysts reaction.

Language: Английский

Citations

10
Visible-Light-Induced Excited-State Copper Catalysis: Recent Advances and Perspectives DOI
Nian Li, Bo Li, Kathiravan Murugesan

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 11974 - 11989

Published: July 26, 2024

Photoactive copper complexes have gained significant attention due to their photocatalytic activities. Different homogeneous Cu(I) complexes, Cu(II) and heterogeneous copper-based photocatalysts been investigated utilized in a broad spectrum of organic transformations. These applications span radical additions, C–C bond C–heteroatom cross-couplings, aerobic oxidative reactions, kinetic resolutions. This review summarizes the advancements this dynamic field visible-light-induced, excited-state copper-catalyzed reactions over recent years. It is organized according type excited species involved provides perspective on current future developments.

Language: Английский

Citations

9
Defluorinative Alkylboration of Alkenes Enabled by Dual Photoredox and Copper Catalysis DOI Open Access

Yanmin Fan,

Zhonghou Huang,

Yi Lu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(5)

Published: Dec. 9, 2023

Abstract A regioselectivity reversed three‐component defluorinative alkylboration of alkenes with trifluoromethyls and bis(pinacolato)diboron via dual photoredox/copper catalysis is reported. The mild conditions are compatible a wide array nonactivated trifluoromethyl aromatics bearing electron‐donating or electron‐neutral substituents, trifluoroacetamides, various terminal internal alkenes, enabling straightforward access to synthetically valuable γ ‐ gem ‐difluoroalkyl boronates high efficiency. Furthermore, this protocol applicable alkene‐tethered furnish ‐difluoromethylene‐containing cyclic compounds. Synthetic applications preliminary mechanistic studies also presented.

Language: Английский

Citations

17
Bifunctional iron-catalyzed alkyne Z-selective hydroalkylation and tandem Z-E inversion via radical molding and flipping DOI Creative Commons
Yongqiang Zhang,

Dongmin Fu,

Ziyang Chen

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Oct. 4, 2024

The challenging synthesis of thermodynamic-unfavored cis-olefins through catalytic cross-coupling reactions requires the synergistic interaction substrate-activating units and configuration-regulating catalysts. Successfully hitting these two birds with one stone, we herein develop a convenient photoredox access to Z-alkenes from alkynes light alkanes bifunctional iron-catalyzed system possessing both C(sp

Language: Английский

Citations

6