Cobalt Complexes Featuring N,O‐Bidentate Ligands with N‐Oxide Moieties: Synthesis, Characterization and Catalytic Activity in Acceptorless Dehydrogenative Coupling of Benzylic Alcohols with Aryl Amines DOI
Xuefeng Jia, Yinghua Yan, Chen Yang

и другие.

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 25, 2025

Comprehensive Summary The transition metal‐catalyzed acceptorless dehydrogenative coupling of alcohols and amines is one the attractive important strategies for construction C=N bonds from perspective environmental friendliness economy. Herein, we report synthesis four novel phosphine‐free cobalt(II) complexes ( Co‐1 — Co‐4 ) with N,O‐bidentate ligands incorporating N‐oxide units their catalytic activity in benzylic aryl amines. X‐ray diffraction analyses revealed that central cobalt atoms three , Co‐2 were six‐coordinated adopted an octahedral geometry configuration. Catalytic evaluation demonstrated exhibited higher than other complexes. This system could provide a series corresponding imine products good functional groups compatibility high yields. Especially, use inexpensive complexes, along readily accessible featuring moieties, offers significant advantages this reaction.

Язык: Английский

Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions DOI

Adam Cook,

Stephen G. Newman

Chemical Reviews, Год журнала: 2024, Номер 124(9), С. 6078 - 6144

Опубликована: Апрель 17, 2024

Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods their functionalization require them to first be converted into a more activated derivative, while recent years have seen vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can used toward this goal. These broadly classified three categories. Deoxygenative functionalizations, representing derivatization C–O bond, enable alcohol act as leaving group formation new C–C bonds. Etherifications, characterized by O–H represent classical reactivity has been modernized include mild reaction conditions, diverse partners, high selectivities. Lastly, chain reactions described, wherein acts mediator formal C–H alkyl backbone. Each these classes transformation will discussed context intermolecular arylation, alkylation, related reactions, illustrating alcohols harnessed

Язык: Английский

Процитировано

39

Dehydroxylative radical N-glycosylation of heterocycles with 1-hydroxycarbohydrates enabled by copper metallaphotoredox catalysis DOI Creative Commons
Dapeng Liu,

Xiao-Sen Zhang,

Shuai Liu

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Апрель 22, 2024

Abstract N-Glycosylated heterocycles play important roles in biological systems and drug development. The synthesis of these compounds heavily relies on ionic N-glycosylation, which is usually constrained by factors such as labile glycosyl donors, precious metal catalysts, stringent conditions. Herein, we report a dehydroxylative radical method for synthesizing N -glycosides leveraging copper metallaphotoredox catalysis, stable readily available 1-hydroxy carbohydrates are activated direct N-glycosylation. Our employs inexpensive photo- copper- catalysts can tolerate some extent water. reaction exhibits broad substrate scope, encompassing 76 examples, demonstrates high stereoselectivity, favoring 1,2- trans selectivity furanoses α-selectivity pyranoses. It also site-selectivity substrates containing multiple N-atoms. synthetic utility showcased through the late-stage functionalization bioactive pharmaceuticals like Olaparib, Axitinib, Metaxalone. Mechanistic studies prove presence radicals importance catalysis.

Язык: Английский

Процитировано

17

Nickel-catalyzed cross-electrophile coupling of unactivated (hetero)aryl sulfone with aryl bromide DOI
Wenxin Li,

Bo‐Jie Huo,

Jie-Ying Huang

и другие.

Journal of Catalysis, Год журнала: 2024, Номер 430, С. 115359 - 115359

Опубликована: Фев. 1, 2024

Язык: Английский

Процитировано

13

Nickel-catalyzed cross-electrophile couplings of aryl fluorosulfates with vinyl chlorosilanes DOI

Jin-He Na,

Hong-Jian Du,

Jia-Wen Jing

и другие.

Journal of Catalysis, Год журнала: 2024, Номер 437, С. 115636 - 115636

Опубликована: Июль 6, 2024

Язык: Английский

Процитировано

12

Alcohols as Alkyl Synthons Enabled by Photoredox-Catalyzed Deoxygenative Activation DOI

Tanumoy Mandal,

Samrat Mallick,

Malekul Islam

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(17), С. 13451 - 13496

Опубликована: Авг. 26, 2024

Alcohols are abundant with versatile structural variety and have ample use as pivotal functional groups in numerous organic processes. Because of their frequent occurrence enumerable natural products, bioactive molecules, medicinal components, alcohol functionalities provide a promising scope research to advance the operational diversity for improving clinical success. Recent years witnessed design modern C–C C–heteroatom bond-forming approaches easily accessible commercially available unactivated aliphatic alcohols native adaptive sp3 handles, hence offering groundbreaking transformative pathways functionalization complex molecular architectures. The judicial application appropriate activating generate alkyl radical from through C–O bond fragmentation employ it potential alkylating agent unfolds unique synthetic strategies, thereby replacing obvious requirement halides. This review elaborately discusses recent trends regarding using C(sp3)-centered various chemical transformations by exploiting different activation modes disrupter under photoredox catalysis. presentation is organized nature scaffolds, kind formation, progress achieved this domain since original discovery providing illustrative examples mechanistic details, focus on difficulties future prospects.

Язык: Английский

Процитировано

10

One-Pot Chlorination and Cross-Electrophile Coupling of Alcohols with Aryl Chlorides DOI
Benjamin N. Ahern, Daniel J. Weix

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 24, 2025

Although alkyl alcohols and aryl chlorides are the two most abundant substrate pools for cross-electrophile coupling, methods to couple them remain limited. Herein we demonstrate a simple procedure in situ deoxychlorination of followed by XEC with chlorides. A broad scope can be achieved tuning rate reaction via halide exchange. Key success is identification 1-chloro-N,N,2-trimethyl-1-propenylamine as mild, noninterfering halogenation reagent.

Язык: Английский

Процитировано

2

Direct Cross-Couplings of Aryl Nonaflates with Aryl Bromides under Nickel Catalysis DOI
Hao Xu,

Jia-Wen Jing,

Yubing Chen

и другие.

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

Опубликована: Янв. 30, 2025

The direct cross-couplings of aryl nonaflates with bromides could be successfully accomplished by utilizing nickel as the catalyst, magnesium metal mediator, and lithium chloride additive. reactions proceeded efficiently in THF at room temperature to produce desired biaryls moderate good yields, showing both a reasonable substrate scope functional group tolerance. Additionally, an equally performance realized when reaction was subjected scale-up synthesis. Preliminary study suggested that presumably proceeds through situ formation arylmagnesium reagent key intermediate.

Язык: Английский

Процитировано

2

Nickel‐Catalyzed Cross‐Electrophile Coupling of Triazine Esters with Aryl Bromides DOI Open Access

Xiang Liu,

Cai‐Yu He,

Hao‐Nan Yin

и другие.

Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(24), С. 3539 - 3546

Опубликована: Авг. 19, 2023

Comprehensive Summary Cross‐electrophile coupling of triazine esters with aryl bromides could be facilely accomplished by employing nickel as catalyst, magnesium metal mediator, and lithium chloride additive. The reactions proceeded efficiently in THF at room temperature through C—O bond activation to afford an array structurally different diaryl ketones moderate good yields wide functional group tolerance. Control experiments showed that nickel, magnesium, chloride, are all indispensable for the performance reaction. Preliminary mechanistic exploration indicated situ formed arylmagnesium reagent insertion into bromide might serve key intermediate cross‐coupling. method which avoids utilization moisture‐labile relatively difficult‐to‐obtain organometallics is step‐economical, cost‐efficient, operationally simple, potentially serving attractive alternative documented methods.

Язык: Английский

Процитировано

23

Ni-catalyzed enantioconvergent deoxygenative reductive cross-coupling of unactivated alkyl alcohols and aryl bromides DOI Creative Commons

L Zhang,

Yu-Zhong Gao,

S. CAI

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Март 28, 2024

Abstract Transition metal-catalyzed enantioconvergent cross-coupling of an alkyl precursor presents a promising method for producing enantioenriched C(sp 3 ) molecules. Because alcohol is ubiquitous and abundant family feedstock in nature, the direct reductive coupling aryl halide enables efficient access to valuable compounds. Although several strategies have been developed overcome high bond dissociation energy C − O bond, asymmetric pattern remains unknown. In this report, we describe realization deoxygenative unactivated (β-hydroxy ketone) bromide presence NHC activating agent. The approach can accommodate substituents various sizes functional groups, its synthetic potency demonstrated through gram scale reaction derivatizations into other compound families. Finally, apply our convergent synthesis four β-aryl ketones that are natural products or bioactive

Язык: Английский

Процитировано

7

Cross-Electrophile Couplings of Benzyl Sulfonium Salts with Thiosulfonates via C–S Bond Activation DOI

Xuan-Bo Hu,

Yuwei Chen, Chenlong Zhu

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(18), С. 13601 - 13607

Опубликована: Сен. 4, 2024

A zinc-mediated cross-electrophile coupling of benzyl sulfonium salts with thiosulfonates via C-S bond cleavage was achieved. The reductive thiolation proceeded well under transition metal-free conditions to afford the desired sulfides in good yields, exhibiting both broad substrate scope and functionality tolerance. In addition, reaction could be applied use selenosulfonate as an effective selenylation agent subjected scale-up synthesis.

Язык: Английский

Процитировано

7