Regioselective, Lewis Acid-Catalyzed Ring-Openings of 2,3-Aziridyl Alcohols with Azoles DOI
Bin Zheng, Mark S. Taylor

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 25, 2025

Methods for regioselective ring-opening reactions of N-sulfonyl-protected aziridyl alcohols with azole nucleophiles have been developed. Several classes azoles, including indazole, substituted pyrazole, benzotriazole, and tetrazole, employed as reaction partners, giving rise to C3-selective opening >3:1 N-selectivity. BF3•OEt2 is the optimal catalyst most substrate combinations, although examples where diphenylborinic acid (Ph2BOH) provides higher yields, or proceed efficiently without a catalyst, are also described. Computational modeling BF3•OEt2-catalyzed consistent observed regiochemical outcome. The calculated transition state appears be stabilized by an unconventional OH···FB hydrogen-bonding interaction.

Язык: Английский

Radical C(sp3)–H functionalization and cross-coupling reactions DOI
Dung L. Golden, Sung‐Eun Suh, Shannon S. Stahl

и другие.

Nature Reviews Chemistry, Год журнала: 2022, Номер 6(6), С. 405 - 427

Опубликована: Май 17, 2022

Язык: Английский

Процитировано

186
Azolation of Benzylic C–H Bonds via Photoredox-Catalyzed Carbocation Generation DOI
Mrinmoy Das,

Leila Zamani,

Christopher Bratcher

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(7), С. 3861 - 3868

Опубликована: Фев. 9, 2023

A visible-light photoredox-catalyzed method is reported that enables the coupling between benzylic C-H substrates and N-H azoles. Classically, medicinally relevant

Язык: Английский

Процитировано

42
Selective functionalization of benzylic C(sp3)–H bonds to synthesize complex molecules DOI Creative Commons
Yu Zhang, Tong Zhang, Shoubhik Das

и другие.

Chem, Год журнала: 2022, Номер 8(12), С. 3175 - 3201

Опубликована: Ноя. 7, 2022

Язык: Английский

Процитировано

51
Copper‐Catalyzed C(sp3)‐Amination of Ketone‐Derived Dihydroquinazolinones by Aromatization‐Driven C−C Bond Scission DOI Creative Commons
Xin‐Yang Lv, Roman Abrams, Rubén Martı́n

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(8)

Опубликована: Дек. 28, 2022

Herein, we describe the development of a copper-catalyzed C(sp3 )-amination proaromatic dihydroquinazolinones derived from ketones. The reaction is enabled by intermediacy open-shell species arising homolytic C-C bond-cleavage driven aromatization. protocol characterized its operational simplicity and generality, including chemical diversification advanced intermediates.

Язык: Английский

Процитировано

44
A photoredox-catalyzed approach for formal hydride abstraction to enable C –H functionalization with nucleophilic partners (F, C, O, N, and Br/Cl) DOI Creative Commons

Yufei Zhang,

Nicholas A. Fitzpatrick,

Mrinmoy Das

и другие.

Chem Catalysis, Год журнала: 2022, Номер 2(2), С. 292 - 308

Опубликована: Янв. 19, 2022

Язык: Английский

Процитировано

42
Benzylic C–H Esterification with Limiting C–H Substrate Enabled by Photochemical Redox Buffering of the Cu Catalyst DOI
Dung L. Golden, Chaofeng Zhang,

Si-Jie Chen

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(17), С. 9434 - 9440

Опубликована: Апрель 21, 2023

Copper-catalyzed radical-relay reactions provide a versatile strategy for selective C-H functionalization; however, with peroxide-based oxidants often require excess substrate. Here, we report photochemical to overcome this limitation by using Cu/2,2'-biquinoline catalyst that supports benzylic esterification limiting Mechanistic studies indicate blue-light irradiation promotes carboxylate-to-copper charge transfer, reducing resting-state CuII CuI, which activates the peroxide generate an alkoxyl radical hydrogen-atom-transfer species. This "photochemical redox buffering" introduces unique sustain activity of Cu catalysts in reactions.

Язык: Английский

Процитировано

38
Enantioselective Intermolecular Radical Amidation and Amination of Benzylic C−H Bonds via Dual Copper and Photocatalysis DOI Creative Commons
Xuemeng Chen, Zhong Lian, Søren Kramer

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(13)

Опубликована: Фев. 1, 2023

A method for direct access to enantioenriched benzylic amides and carbamate-protected primary benzylamines by C-H functionalization is reported. The substrate used as limiting reagent with only a small excess of the unactivated amide or carbamate nucleophile. enantioselective intermolecular dehydrogenative C-N bond formation enabled combination chiral copper catalyst, photocatalyst, an oxidant, it takes place under mild conditions, which allow broad scope. compatible late-stage functionalization, provides easy 15 N-labeled amines starting from cheap NH4 Cl.

Язык: Английский

Процитировано

32
A General Photocatalytic Strategy for Nucleophilic Amination of Primary and Secondary Benzylic C–H Bonds DOI
Madeline E. Ruos, R. Garrison Kinney, Oliver T. Ring

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(33), С. 18487 - 18496

Опубликована: Авг. 11, 2023

We report a visible-light photoredox-catalyzed method that enables nucleophilic amination of primary and secondary benzylic C(sp3)-H bonds. A novel amidyl radical precursor organic photocatalyst operate in tandem to transform bonds into carbocations via sequential hydrogen atom transfer (HAT) oxidative radical-polar crossover. The resulting carbocation can be intercepted by variety N-centered nucleophiles, including nitriles (Ritter reaction), amides, carbamates, sulfonamides, azoles, for the construction pharmaceutically relevant C(sp3)-N under unified reaction conditions. Mechanistic studies indicate HAT is radical-mediated operates reductive quenching pathway. These findings establish mild, metal-free, modular protocol rapid diversification library aminated products.

Язык: Английский

Процитировано

32
Intermolecular Enantioselective Benzylic C(sp3)−H Amination by Cationic Copper Catalysis** DOI

Ling Dai,

Yingying Chen, Li‐Jun Xiao

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(24)

Опубликована: Апрель 14, 2023

Chiral benzylic amines are privileged motifs in pharmacologically active molecules. Intramolecular enantioselective radical C(sp3 )-H functionalization by hydrogen-atom transfer has emerged as a straightforward, powerful tool for the synthesis of chiral amines, but methods intermolecular amination remain elusive. Herein, we report cationic copper catalytic system with peroxide an oxidant. This mild, straightforward method can be used to transform array feedstock alkylarenes and amides into high enantioselectivities, it good functional group tolerance broad substrate scope. More importantly, synthesize bioactive molecules, including drugs. Preliminary mechanistic studies indicate that reaction involves radicals generated transfer.

Язык: Английский

Процитировано

29
Recent advances in C(sp3)–N bond formation via metallaphoto-redox catalysis DOI
Juan Zhang,

Xiao-Die Huan,

Xin Wang

и другие.

Chemical Communications, Год журнала: 2024, Номер 60(50), С. 6340 - 6361

Опубликована: Янв. 1, 2024

In this review, the state-of-the-art advances in radical-involved C(sp 3 )–N bond formation via metallaphotoredox catalysis have been highlighted, which are organized according to different catalytic modes, reaction types, and substrate classes.

Язык: Английский

Процитировано

12