Dinuclear Gold‐Catalyzed para‐Selective C−H Arylation of Undirected Arenes by Noncovalent Interactions DOI Open Access
Duanyang Liu, Jie Han, Kai Liu

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(44)

Опубликована: Сен. 14, 2023

Abstract The regioselectivity of C−H functionalization is commonly achieved by directing groups, electronic factors, or steric hindrance, which facilitate the identification reaction sites. However, such strategies are less effective for reactants as simple monofluoroarenes due to their relatively low reactivity and modest demands fluorine atom. Herein, we present an undirected gold‐catalyzed para ‐C−H arylation a wide array using air‐stable aryl silanes germanes at room temperature. A high ‐regioselectivity (up 98 : 2) can be realized utilizing dinuclear dppm(AuOTs) 2 (dppm=bis(diphenylphosphino)methane) catalyst hexafluorobenzene solvent. This provides general practical protocol concise construction structurally diverse ‐arylated through activation manner. It features excellent functional group tolerance broad substrate scope (>80 examples). Besides, this strategy also robust other monosubstituted arenes heteroarenes. Our mechanistic studies theoretical calculations suggest that selectivity arises from highly electrophilic flexible Ar−Au(III)−Au(I) species, coupled with noncovalent interaction induced hexafluorobenzene.

Язык: Английский

Transition-metal catalyzed C–H activation as a means of synthesizing complex natural products DOI

Soumya Kumar Sinha,

Pintu Ghosh, Shubhanshu Jain

и другие.

Chemical Society Reviews, Год журнала: 2023, Номер 52(21), С. 7461 - 7503

Опубликована: Янв. 1, 2023

Over the past few decades, advent of C–H activation has led to a rethink among chemists about synthetic strategies employed for multi-step transformations.

Язык: Английский

Процитировано

52
Hydrogen-bond-acceptor ligands enable distal C(sp3)–H arylation of free alcohols DOI
Daniel A. Strassfeld, Chia-Yu Chen, Han Seul Park

и другие.

Nature, Год журнала: 2023, Номер 622(7981), С. 80 - 86

Опубликована: Сен. 6, 2023

Язык: Английский

Процитировано

29
Controlling Reactivity and Selectivity in the Nondirected C–H Activation of Arenes with Palladium DOI
Simon Kaltenberger, Manuel van Gemmeren

Accounts of Chemical Research, Год журнала: 2023, Номер 56(18), С. 2459 - 2472

Опубликована: Авг. 24, 2023

ConspectusAromatic structures are widespread motifs throughout organic chemistry, and C-H activation has been recognized as a major tool for enabling their sustainable efficient functionalization. Through activation, arenes can be modified without the need prefunctionalization, leading to inherent atom- step-economic advantages over traditional methods. However, development of synthetically useful methods, several hurdles have overcome. The strength bonds necessitates sufficiently reactive catalysts, while presence multiple within substrate poses challenges in terms site-selectivity. Traditionally these addressed by control. By attaching different directing groups (DGs), reactivity respective arene was significantly enhanced DG guided metal close proximity specific bonds, resulting high introduction removal add additional steps synthetic sequence, scope reaction is limited class. complementary nondirected methods that applied broad range necessity carry functional group coordinates Pd (referred simple arenes) therefore highly desirable. intrinsically lower such substrates absence selectivity-determining pose significant solved only catalysts. Consequently, field especially with respect Pd-catalyzed remained comparatively underdeveloped when we initiated our research program 2017. At time, state-of-the-art required used large excess, precluding its use late-stage Since organopalladium species among most versatile intermediates, realized developing system, which effectively selectively activate limiting reagent, would powerful chemistry. This account summarizes groups' toward application catalytic systems offering this desired focuses explicitly on functionalization reactions arenes, where employed reagent. After an state before 2017 associated challenges, experimental mechanistic details about first arene-limited, palladium will discussed. enabled identification combination two ligands, N-heterocycle amino acid-derived ligand. Afterward discuss expansion dual-ligand approach further arene-limited transformations. Finally, describe methodologies originated from observations made during studies, namely, deuteration selective olefination method uses noncovalent interactions induce meta selectivity.

Язык: Английский

Процитировано

24
The crucial role of silver(i)-salts as additives in C–H activation reactions: overall analysis of their versatility and applicability DOI Creative Commons
Renato L. Carvalho, Emilay B. T. Diogo, Simon L. Homölle

и другие.

Chemical Society Reviews, Год журнала: 2023, Номер 52(18), С. 6359 - 6378

Опубликована: Янв. 1, 2023

This review discusses the important role of silver( i ) salts as additives in transition-metal catalyzed C–H activation, and depicts discussion about current shift towards Ag-free procedures, plausible sustainable alternatives.

Язык: Английский

Процитировано

20
Amino Acid-Derived Ionic Chiral Catalysts Enable Desymmetrizing Cross-Coupling to Remote Acyclic Quaternary Stereocenters DOI Creative Commons
Junqiang Wei, Vincent Gandon, Ye Zhu

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(30), С. 16796 - 16811

Опубликована: Июль 20, 2023

Synthetic application of asymmetric catalysis relies on strategic alignment bond construction to creation chirality a target molecule. Remote desymmetrization offers distinctive advantages spatial decoupling catalytic transformation and generation stereogenic element. However, such separation presents substantial difficulties for the chiral catalyst discriminate distant enantiotopic sites through reaction three or more bonds away from prochirality center. Here, we report strategy that establishes acyclic quaternary carbon stereocenters cross-coupling reactions at distal positions aryl substituents. The new class amino acid-derived ionic catalysts enables desymmetrizing (enantiotopic-group-selective) Suzuki-Miyaura reaction, Sonogashira Buchwald-Hartwig amination between diverse diarylmethane scaffolds aryl, alkynyl, coupling partners, providing rapid access enantioenriched molecules project substituents widely spaced in three-dimensional space. Experimental computational investigations reveal electrostatic steering substrates by C-terminus ligands interactions. Cooperative ion-dipole interactions catalyst's amide group potassium cation aid preorganization transmits asymmetry product. This study demonstrates it is practical achieve precise long-range stereocontrol engineering arrangements catalysts' substrate-recognizing groups metal centers.

Язык: Английский

Процитировано

18
Enhancing Substrate–Metal Catalyst Affinity via Hydrogen Bonding: Pd(II)-Catalyzed β-C(sp3)–H Bromination of Free Carboxylic Acids DOI
Liang Hu, Guangrong Meng, Xiangyang Chen

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(30), С. 16297 - 16304

Опубликована: Июль 24, 2023

The achievement of sufficient substrate-metal catalyst affinity is a fundamental challenge for the development synthetically useful C-H activation reactions weakly coordinating native substrates. While hydrogen bonding has been harnessed to bias site selectivity in existing C(sp2)-H reactions, potential designing catalysts with bond donors (HBDs) enhance catalyst-substrate and, thereby, facilitate otherwise unreactive C(sp3)-H remains be demonstrated. Herein, we report discovery ligand scaffold containing remote amide motif that can form favorable meta-macrocyclic interaction aliphatic acid substrate. utility this demonstrated through an unprecedented bromination α-tertiary and α-quaternary free carboxylic acids, which proceeds exceedingly high mono-selectivity. geometric relationship between NHAc donor quinoline crucial forming meta-macrocyclophane-like interaction, provides guideline future design employing secondary interactions.

Язык: Английский

Процитировано

18
Electrochemically synthesized polyanine@Cu-BTC MOF as a bifunctional matrix for aptasensing of tetracycline in aquatic products DOI
Feng Zhan,

Yanan Zhao,

Xiaohui Dai

и другие.

Microchemical Journal, Год журнала: 2023, Номер 196, С. 109512 - 109512

Опубликована: Окт. 20, 2023

Язык: Английский

Процитировано

13
Inherently chiral resorcinarene cavitands through ionic catalyst-controlled cross-coupling DOI Creative Commons
Mingfeng Li,

Clement Kim Soon Ho,

Ivan Keng Wee On

и другие.

Chem, Год журнала: 2024, Номер 10(11), С. 3323 - 3341

Опубликована: Июль 5, 2024

Cavitands have emerged as privileged architectures in supramolecular chemistry. Nonetheless, achieving structural diversity and tunability through heterofunctionalization along the rims of macrocycles has remained a formidable challenge. As rudimental example, stepwise conversion C4v-symmetric scaffolds to inherently chiral ABCD patterns is synthetically impractical owing low theoretical yields (0.8%) need for chromatographic enantioseparation.Herein, we report catalytic desymmetrization strategy access cavitands. Through engineering ionic palladium catalysts, diverse functionalities, including aryl, alkenyl, alkynyl, amino groups, can be installed on large with high site- stereoselectivity. An adaptable protocol been established furnish designer ABCD-type cavitands accordance choreography coupling partners. Experimental computational studies reveal synergistic electrostatic steering catalysis by catalyst–substrate interactions.

Язык: Английский

Процитировано

5
Bifunctional NHC-Promoted C2-Alkylation of Pyridine via Ni–Al Bimetallic-Catalyzed Hydroarylation of Unactivated Alkenes DOI
Binyang Jiang, Jiaming Liu, Shi‐Liang Shi

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(9), С. 6068 - 6075

Опубликована: Апрель 18, 2023

Achieving site-selective alkylation with pyridine under transition metal catalysis has remained a long-standing challenge, especially when using unactivated alkene as an alkylating reagent. We herein describe C2-alkylation of Ni–Al bimetallic and directing bifunctional N-heterocyclic carbene (NHC) ligand through hydroarylation alkenes. A broad range C2-alkylated pyridines various functionalities could be prepared in high efficiency (up to 99% yield) C2-selectivity, the scope heterocycles is not limited but can expanded other azines like pyrazines pyrimidines. Mechanistic studies suggest that NHC–Ni–Al–pyridine complex responsible for site selectivity control reductive elimination might rate-determining step.

Язык: Английский

Процитировано

12
Spirobipyridine Ligands as a Unique Platform for Substrate Recognition and Reaction Control through Noncovalent Interactions DOI
Sobi Asako, Laurean Ilies

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 6372 - 6379

Опубликована: Апрель 4, 2025

Язык: Английский

Процитировано

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