Ligand Effects in Carboxylic Ester- and Aldehyde-Assisted β-C–H Activation in Regiodivergent and Enantioselective Cycloisomerization–Hydroalkenylation and Cycloisomerization–Hydroarylation, and [2 + 2 + 2]-Cycloadditions of 1,6-Enynes DOI
Kiron Kumar Ghosh, T. V. RajanBabu

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(27), С. 18753 - 18770

Опубликована: Июнь 27, 2024

Herein, we report room temperature, atom-economic protocols for high regio- and enantioselective tandem cycloisomerization–hydroarylation cycloisomerization–hydroalkenylation of 1,6-enynes leading to vicinal carba-functionalized pyrrolidines, tetrahydrofurans, cyclopentanes. The latter steps in these processes involve carbonyl-coordination-assisted ortho-C–H activation aromatic aldehydes esters, and, a similar, yet rarely seen, β-C–H the case acrylates. Synthetically useful versions such reactions are rare limited C2–H indoles pyrroles. A similar reaction is also observed with N-vinylphthalimide, which has carbonyl group suitable C–H activation. dibenzooxaphosphole ligand, (2S,2S′,3S,3S′)-MeO-BIBOP was uniquely identified as crucial achieving challenging enantioselectivity. This methodology gives access substituted five-membered carbo- heterocyclic compounds good yields excellent enantioselectivities under low catalyst loading. primary KIE 3.5 an intermolecular competition experiment methyl benzoate d5-methyl benzoate, indicates that cleavage turnover-limiting step this process. Unlike acrylates, undergoes exclusive hydroalkenylation, β, γ-unsaturated ester, but-3-enoate, highly cycloisomerization-coupling sequence 1,6-enyne giving either [2 + 2 2]-cycloaddition (S, S)-BDPP or hydroalkenylation (2S,2′S,3S,3′S)-MeO-BIBOP depending on ligand employed. (E)-configuration newly formed double bond at terminal alkynyl carbon (of starting enyne) product β,γ-unsaturated ester suggests more classical migratory insertion-β-hydride elimination route formation product.

Язык: Английский

Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling DOI
Yudong Yang, Yimin Wu, Zhengyang Bin

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(2), С. 1224 - 1243

Опубликована: Янв. 4, 2024

Efficient and streamlined synthetic methods that facilitate the rapid build-up of structurally diverse π-conjugated systems are paramount importance in quest for organic optoelectronic materials. Among these methods, transition-metal-catalyzed oxidative Ar–H/Ar–H coupling reactions between two (hetero)arenes have emerged as a concise effective approach generating wide array bi(hetero)aryl fused heteroaryl structures. This innovative bypasses challenges associated with substrate pre-activation processes, thereby allowing creation frameworks were previously beyond reach using conventional Ar–X/Ar–M reactions. These inherent advantages ushered new design patterns molecules deviate from traditional methods. ground-breaking enables transcendence limitations repetitive material structures, ultimately leading to discovery novel high-performance In this Perspective, we provide an overview recent advances development materials through utilization We introduce several notable strategies domain, covering both directed non-directed strategies, dual chelation-assisted strategy ortho-C–H arylation/cyclization strategy. Additionally, shed light on role advancement Finally, discuss current existing protocols offer insights into future prospects field.

Язык: Английский

Процитировано

21
C–H activation-initiated spiroannulation reactions and their applications in the synthesis of spirocyclic compounds DOI

Qianting Zhou,

Bin Li, Xinying Zhang

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(12), С. 2324 - 2338

Опубликована: Янв. 1, 2024

This review summarizes the most recent progress made in C–H bond activation-initiated spiroannulation reactions and their applications construction of structurally diverse biologically valuable spirocyclic scaffolds.

Язык: Английский

Процитировано

21
Electrooxidative Rhodium(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective C−H Annulation of Sulfoximines with Alkynes DOI
Gang Zhou, Tao Zhou,

Ao‐Lian Jiang

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(15)

Опубликована: Янв. 30, 2024

Abstract The combination of achiral Cp*Rh(III) with chiral carboxylic acids (CCAs) represents an efficient catalytic system in transition metal‐catalyzed enantioselective C−H activation. However, this hybrid catalysis is limited to redox‐neutral activation reactions and the adopt oxidative remains elusive pose a significant challenge. Herein, we describe development electrochemical Cp*Rh(III)‐catalyzed annulation sulfoximines alkynes enabled by acid (CCA) operationally friendly undivided cell at room temperature. A broad range enantioenriched 1,2‐benzothiazines are obtained high yields excellent enantioselectivities (up 99 % yield 98 : 2 er). practicality method demonstrated scale‐up reaction batch reactor external circulation. crucial intermediate isolated, characterized, transformed, providing rational support for Rh(III)/Rh(I) electrocatalytic cycle.

Язык: Английский

Процитировано

20
Rh(III)-Catalyzed [3 + 2] Annulation/Pinacol Rearrangement Reaction of Enaminones with Iodonium Ylides: Direct Synthesis of 2-Spirocyclo-pyrrol-3-ones DOI

Mingshuai Zhang,

Longkun Chen,

Haifeng Sun

и другие.

Organic Letters, Год журнала: 2023, Номер 25(39), С. 7214 - 7219

Опубликована: Сен. 26, 2023

A novel Rh(III)-catalyzed cascade alkenyl C-H activation/[3 + 2] annulation/pinacol rearrangement reaction of enaminones with iodonium ylides has been developed. This methodology provides a new and straightforward synthetic strategy to afford highly functionalized 2-spirocyclo-pyrrol-3-ones in satisfactory yield from readily available starting materials under mild conditions. Moreover, gram-scale reactions further derivatization experiments are implemented demonstrate the potential utility this developed approach.

Язык: Английский

Процитировано

33
Copper/BINOL-Catalyzed Enantioselective C–H Functionalization toward Planar Chiral Ferrocenes Under Mild Conditions DOI
Zhuo‐Zhuo Zhang, Gang Zhou, Qiang Yue

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(6), С. 4030 - 4039

Опубликована: Фев. 28, 2024

Copper-catalyzed enantioselective C–H activation proceeding through an inner-sphere mechanism remains a huge challenge. Herein, copper-catalyzed alkynylation with terminal alkynes assisted by 8-aminoquinoline using readily available (S)-BINOL as the chiral ligand was disclosed. The reaction proceeded under mild conditions catalytic amount of copper salt, providing range ferrocenes in good yields and enantioselectivities (0 °C, up to 77% yield 94% ee). alteration stoichiometric chemical oxidant renewable electricity is also feasible at ambient temperature, demonstrating robustness this copper/BINOL catalysis. Notably, first cupraelectrocatalyzed reaction. Gram-scale synthesis, versatile transformations, application resulting oxazoline–olefin asymmetric synthesis highlight utility protocols.

Язык: Английский

Процитировано

15
Expedient Synthesis of Axially and Centrally Chiral Diaryl Ethers via Cobalt-Catalyzed Photoreductive Desymmetrization DOI
Yishou Wang,

Ruijie Mi,

Songjie Yu

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 4638 - 4647

Опубликована: Март 12, 2024

Axially chiral diaryl ethers make up a unique class of atropisomers bearing restricted rotation about the C–O bond. Methods for expedient synthesis axially ether-based structures have been largely underdeveloped. Herein, we developed an efficient metal-catalyzed desymmetrization strategy to unveil formation and centrally dual in high diastereo- enantioselectivity. The protocol leverages cobalt-catalyzed photoreductive enantioselective couplings dialdehyde alkyne deliver stereogenicity, ether scaffold is equipped with useful synthetic handles including formyl, hydroxyl, allyl groups, as has demonstrated carboxylic acid potential ligand asymmetric catalysis.

Язык: Английский

Процитировано

15
Recent advances in Rh(i)-catalyzed enantioselective C–H functionalization DOI Creative Commons
Yue Zhang, Jing‐Jing Zhang, Lujun Lou

и другие.

Chemical Society Reviews, Год журнала: 2024, Номер 53(7), С. 3457 - 3484

Опубликована: Янв. 1, 2024

Chiral carbon-carbon (C-C) and carbon-heteroatom (C-X) bonds are pervasive very essential in natural products, bioactive molecules, functional materials, their catalytic construction has emerged as one of the hottest research fields synthetic organic chemistry. The last decade witnessed vigorous progress Rh(I)-catalyzed asymmetric C-H functionalization a complement to Rh(II) Rh(III) catalysis. This review aims provide most comprehensive up-to-date summary covering recent advances activation for functionalization. In addition development diverse reactions, chiral ligand design mechanistic investigation (inner-sphere mechanism, outer-sphere 1,4-Rh migration) will also be highlighted.

Язык: Английский

Процитировано

13
Rh(III)-Catalyzed Atroposelective C–H Selenylation of 1-Aryl Isoquinolines DOI

Dong‐Song Zheng,

Pei‐Pei Xie,

Fangnuo Zhao

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 6009 - 6015

Опубликована: Апрель 5, 2024

Rhodium(III)-catalyzed atroposelective C–H selenylation of 1-aryl isoquinolines has been achieved. The direct reaction between and 2-(phenylselanyl)isoindoline-1,3-dione in the presence chiral SCpRh(III) complex afforded a series axially isoquinoline selenides up to 95% yield 96% ee. features mild conditions broad substrate scope. DFT calculations revealed that C–Se bond formation step proceeds through formal SN2 pathway.

Язык: Английский

Процитировано

12
Enantioselective Rhodium‐Catalyzed C−H Arylation Enables Direct Synthesis of Atropisomeric Phosphines DOI
Zexian Li,

Weipeng Xu,

Shuaishuai Song

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(8)

Опубликована: Янв. 6, 2024

Atropisomeric phosphines hold considerable significance in asymmetric catalysis, yet their synthesis presents a formidable challenge owing to intricate multistep procedures. In this context, groundbreaking methodology has been presented for preparation. This innovative approach entails an atroposelective rhodium-catalyzed C-H activation employing aryl and heteroaryl halides, chelated by P(III) center. The essence of strategy lies its ability directly construct chiral phosphine ligands single step, thereby exhibiting exceptional efficiency terms atom redox economy. Illustrative examples serve demonstrate the immense potential situ-formed catalysis. Mechanistic experiments have further provided invaluable insights into transformation.

Язык: Английский

Процитировано

10
Mechanisms of C(sp3)–H and C=C selective oxidative heterofunctionalizations by non-heme Fe and Mn mimics of oxygenase enzymes DOI
Konstantin P. Bryliakov

Coordination Chemistry Reviews, Год журнала: 2024, Номер 508, С. 215793 - 215793

Опубликована: Март 18, 2024

Язык: Английский

Процитировано

9