Efficient Synthesis of Sulfur-Stereogenic Sulfoximines via Ru(II)-Catalyzed Enantioselective C–H Functionalization Enabled by Chiral Carboxylic Acid

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(18), С. 6810 - 6816

Опубликована: Апрель 28, 2021

Ru(II)-catalyzed enantioselective C-H functionalization involving an enantiodetermining cleavage step remains undeveloped. Here we describe a activation/annulation of sulfoximines with α-carbonyl sulfoxonium ylides using novel class chiral binaphthyl monocarboxylic acids as ligands, which can be easily and modularly prepared from 1,1'-binaphthyl-2,2'-dicarboxylic acid. A broad range sulfur-stereogenic were in high yields excellent enantioselectivities (up to 99% yield ee) via desymmetrization, kinetic resolution, parallel resolution. Furthermore, the resolution products transformed sulfoxides key intermediates for kinase inhibitors.

Язык: Английский

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Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

ACS Catalysis, Год журнала: 2022, Номер 12(6), С. 3452 - 3506

Опубликована: Март 3, 2022

Transition-metal-catalyzed C–H bond functionalizations have had an enormous influence on organic synthesis in recent times. However, the use of low-abundance 4d and 5d metals is almost inevitable, they are high demand. This will be a cause concern, hence, it important to develop methods based 3d metals, which widely present Earth's crust. In this regard, metal catalysts or their precursors for catalysis, general, functionalizations, particular, has gained significant momentum The major development catalytic with been achieved predominantly strongly coordinating directing groups such as pyridyl, pyrimidinyl, pyrazolyl, 8-amino-quinolinyl groups. Thus, prefunctionalization substrates these necessary, contradicts step- atom-economy activation. commonly available functional aldehyde, ketone, carboxylic acid, amide, hydroxy, N-oxides loosely bind through weak-coordination. These weakly orient activate regioselectively without need preinstalled Although challenging, contemporary topic actively pursued by many researchers Through article, we provide comprehensive overview metal-catalyzed, coordinating, directing-group-enabled reported until March 2021.

Язык: Английский

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DFT Study on Mechanism and Regioselectivity in Pd(II)‐Catalyzed Dehydrogenative Heck Olefination of Selenophenes

ChemistrySelect, Год журнала: 2025, Номер 10(4)

Опубликована: Янв. 1, 2025

Abstract The present study deals with the theoretical investigation of mechanistic and regiochemical aspects Pd(II)‐catalyzed dehydrogenative Heck olefination selenophenes. detailed reaction mechanism was established, roles catalyst regioselectivity were well rationalized. Our results clearly showed that whole involves a concerted metalation‐deprotonation (CMD) process between C 2 site selenophene Pd(OAc) in first catalytic cycle. Afterward, olefin coordinates to palladium, followed by regioselective 1,2‐migratory insertion form C─C bond. Then, β ‐hydride elimination would give final 2‐monoolefinated product. Subsequently, second cycle generates symmetrical 2,5‐diolefinated Another key finding this is its monoolefinated product act as nucleophiles, while behaves an electrophile. A global reactivity index (GRI) analysis revealed nucleophilicity ( N k ) , 3 4 5 atoms plays important role controlling selectivity at these sites. However, distortion energies play more reactions

Язык: Английский

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Ruthenium-Catalyzed Enantioselective C–H Functionalization: A Practical Access to Optically Active Indoline Derivatives

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(40), С. 15730 - 15736

Опубликована: Сен. 19, 2019

Ru(II)-catalyzed enantioselective C–H activation/hydroarylation has been developed for the first time, allowing highly synthesis of indoline derivatives via catalytic activation. Commercially available Ru(II) arene complexes and chiral α-methylamines were employed as catalysts. Based on a sterically rigidified transient directing group, multisubstituted indolines produced in up to 92% yield with 96% ee. Further transformation resulting 4-formylindoline enables access an optically active tricyclic compound that is potential biological pharmaceutical interest.

Язык: Английский

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Ruthenium(II)‐Catalyzed Asymmetric Inert C−H Bond Activation Assisted by a Chiral Transient Directing Group

Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(9), С. 3475 - 3479

Опубликована: Дек. 23, 2019

Abstract A ruthenium(II)‐catalyzed asymmetric intramolecular hydroarylation assisted by a chiral transient directing group has been developed. series of 2,3‐dihydrobenzofurans bearing all‐carbon quaternary stereocenters have prepared in remarkably high yields (up to 98 %) and enantioselectivities >99 % ee ). By this methodology, novel total synthesis CB2 receptor agonist MDA7 successfully

Язык: Английский

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Reactivity-Controlling Factors in Carboxylate-Assisted C–H Activation under 4d and 3d Transition Metal Catalysis

ACS Catalysis, Год журнала: 2020, Номер 10(18), С. 10551 - 10558

Опубликована: Авг. 17, 2020

Detailed density functional theory calculations provide valuable insight into reactivity-controlling factors in transition metal-catalyzed C–H activation by carboxylate assistance. The chelation-assisted of a variety arenes 3d and 4d metal complexes was analyzed means bond order analysis through (DFT) as well energy decomposition DLPNO–CCSD(T) calculations, thereby providing in-depth information on distinct electronic influences the key state demonstrating preferred base-assisted internal electrophilic substitution (BIES) rather than concerted metalation-deprotonation (CMD) pathway.

Язык: Английский

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Recent Advances in C–H Bond Functionalization with Ruthenium-Based Catalysts

Catalysts, Год журнала: 2019, Номер 9(2), С. 173 - 173

Опубликована: Фев. 12, 2019

The past decades have witnessed rapid development in organic synthesis via catalysis, particularly the reactions through C–H bond functionalization. Transition metals such as Pd, Rh and Ru constitute a crucial catalyst these functionalization reactions. This process is highly attractive not only because it saves reaction time reduces waste,but also, more importantly, allows to be performed region specific manner. Indeed, several compounds could readily accessed with transition metals. In recent past, tremendous progress has been made on ruthenium including less expensive but stable ruthenium(II) catalysts. ruthenium-catalysed functionalization, viz. arylation, alkenylation, annulation, oxygenation, halogenation involving C–C, C–O, C–N, C–X forming reactions, described presented numerous reviews. review discusses of various ruthenium-based first section presents arylation covering directed by N–Heteroaryl groups, oxidative dehydrative decarboxylative sp3-C–H Subsequently, alkylation, allylation alkenylation meta-selective alkylation presented. Finally, annulation arenes alkynes C–H/O–H or C–H/N–H cleavage discussed.

Язык: Английский

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Late-Stage Diversification by Selectivity Switch in meta-C–H Activation: Evidence for Singlet Stabilization

ACS Catalysis, Год журнала: 2019, Номер 10(1), С. 435 - 440

Опубликована: Ноя. 25, 2019

The full control of site selectivity in C–H activation is paramount for the programmed late-stage functionalization structurally complex structures. During past decade, directing groups have revolutionized molecular synthesis terms ortho-selective activation. In sharp contrast, a switch that guides typical ortho- to remote meta-C–H has thus far proven elusive. Herein, we describe realization such concept robust ruthenium catalysis. distal transformation was guided by key mechanistic insights into mild, synergistic action carboxylates and phosphines ruthenium(II) Our findings allowed broadly effective diversification drugs natural product molecules, tolerating sensitive fluorescent dyes, drugs, lipids, peptides, nucleosides, carbohydrates.

Язык: Английский

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Ruthenium-catalyzed C–H bond functionalization in cascade and one-pot transformations

Coordination Chemistry Reviews, Год журнала: 2020, Номер 428, С. 213602 - 213602

Опубликована: Окт. 15, 2020

Язык: Английский

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Dual-Ligand-Enabled Ir(III)-Catalyzed Enantioselective C–H Amidation for the Synthesis of Chiral Sulfoxides

ACS Catalysis, Год журнала: 2020, Номер 10(13), С. 7207 - 7215

Опубликована: Июнь 15, 2020

A rational designed Ir(III)-catalyzed enantioselective C–H amidation of dibenzyl sulfoxides through desymmetrization and parallel kinetic resolution is demonstrated. An Ir(III) complex equipped with a t-butyl cyclopentadienyl ligand paired modified chiral proline enables the highly sulfoxide-steered bond activation, providing an efficient straightforward way to construct sulfur centers. wide range dioxazolones are compatible this process, giving access variety functionalized sulfoxide compounds synthetically attractive amide substitution groups in good yields enantioselectivities. Moreover, flexible derivatization amidated was elaborated, various types scaffolds that would be potentially useful asymmetric catalysis as bidentate tridentate ligands.

Язык: Английский

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