Catalytic atroposelective synthesis

Nature Catalysis, Год журнала: 2024, Номер 7(5), С. 483 - 498

Опубликована: Апрель 30, 2024

Язык: Английский

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Dual-Catalyzed Stereodivergent Electrooxidative Homocoupling of Benzoxazolyl Acetate

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(2), С. 1522 - 1531

Опубликована: Янв. 3, 2024

The development of a reliable strategy for stereodivergent radical reactions that allows convenient access to all stereoisomers homocoupling adducts with multiple stereogenic centers remains an unmet goal in organic synthesis. Herein, we describe dual-catalyzed electrooxidative C(sp3)–H/C(sp3)–H complete absolute and relative stereocontrol the synthesis molecules contiguous quaternary stereocenters general predictable manner. reaction is achieved by synergistically utilizing two distinct chiral catalysts convert identical racemic substrates into inherently distinctive reactive intermediates, dictate enantioselective addition, allow full complement stereoisomeric products via simple catalyst permutation. successful execution dual-electrocatalytic programmed activation provides significant conceptual advantage will serve as useful foundation further research cooperative stereocontrolled transformations diversity-oriented

Язык: Английский

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Single‐Atom Iron Catalyst as an Advanced Redox Mediator for Anodic Oxidation of Organic Electrosynthesis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(27)

Опубликована: Апрель 23, 2024

Homogeneous electrocatalysts can indirect oxidate the high overpotential substrates through single-electron transfer on electrode surface, enabling efficient operation of organic electrosynthesis catalytic cycles. However, problems this chemistry still exist such as dosage, difficult recovery, and low efficiency. Single-atom catalysts (SACs) exhibit atom utilization excellent activity, hold great promise in addressing limitations homogeneous catalysts. In view this, we have employed Fe-SA@NC an advanced redox mediator to try change situation. was synthesized using encapsulation-pyrolysis method, it demonstrated remarkable performance a range reported reactions, construction various C-C/C-X bonds. Moreover, potential exploring new synthetic method for electrosynthesis. We develop electro-oxidative ring-opening transformation cyclopropyl amides. reaction system, showed good tolerance drug molecules with complex structures, well flow electrochemical syntheses gram-scale transformations. This work highlights SACs electrosynthesis, thereby opening avenue chemistry.

Язык: Английский

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Efficient Proton Transfer and Charge Separation within Covalent Organic Frameworks via Hydrogen-Bonding Network to Boost H₂O₂ Photosynthesis

Nano Letters, Год журнала: 2024, Номер 24(21), С. 6302 - 6311

Опубликована: Май 15, 2024

Photocatalytic synthesis based on the oxygen reduction reaction (ORR) has shown great promise for H2O2 production. However, low activity and selectivity of 2e– ORR result in a fairly efficiency Herein, we propose strategy to enhance proton-coupled electron transfer (PCET) process covalent organic frameworks (COFs), thereby significantly boosting photosynthesis. We demonstrated that construction hydrogen-bonding network, achieved by anchoring H3PO4 molecular network COF nanochannels, can greatly improve both proton conductivity photogenerated charge separation COFs. Thus, COF@H3PO4 exhibited superior photocatalytic performance generating without sacrificial agents, with solar-to-chemical conversion as high 0.69%. Results indicated much more localized spatial distribution energy band density led efficient separation, small barrier rate-limiting step from *OOH endowed higher selectivity.

Язык: Английский

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Programmed alternating current optimization of Cu-catalyzed C-H bond transformations

Science, Год журнала: 2024, Номер 385(6705), С. 216 - 223

Опубликована: Июль 11, 2024

Direct current (DC) electrosynthesis, which has undergone optimization over the past century, plays a pivotal role in variety of industrial processes. Alternating (AC) characterized by polarity reversal and periodic fluctuations, may be advantageous for multiple chemical reactions, but apparatus, principles, application scenarios remain underdeveloped. In this work, we introduce protocol programmed AC (pAC) electrosynthesis that systematically adjusts currents, frequencies, duty ratios. The representative pAC waveforms facilitates copper-catalyzed carbon-hydrogen bond cleavage cross-coupling difunctionalization reactions exhibit suboptimal performance under DC oxidation conditions. Moreover, observing catalyst dynamic variation diverse waveform applications provides mechanistic insight.

Язык: Английский

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Cobalt‐Catalyzed Enantioselective C−H Carbonylation towards Chiral Isoindolinones

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(10)

Опубликована: Янв. 11, 2024

Transition metal-catalyzed enantioselective C-H carbonylation with carbon monoxide, an essential and easily available C1 feedstock, remains challenging. Here, we disclosed unprecedented catalyzed by inexpensive readily cobalt(II) salt. The reactions proceed efficiently through desymmetrization, kinetic resolution, parallel affording a broad range of chiral isoindolinones in good yields excellent enantioselectivities (up to 92 % yield 99 ee). synthetic potential this method was demonstrated asymmetric synthesis biological active compounds, such as (S)-PD172938 (S)-Pazinaclone. resulting also serve ligands cobalt-catalyzed annulation alkynes construct phosphorus stereocenter.

Язык: Английский

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Atroposelective catalysis

Nature Reviews Chemistry, Год журнала: 2024, Номер 8(7), С. 497 - 517

Опубликована: Июнь 18, 2024

Язык: Английский

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Electrooxidative Rhodium(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective C−H Annulation of Sulfoximines with Alkynes

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

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Cobalt‐Catalyzed Asymmetric Aza‐Nozaki–Hiyama–Kishi (NHK) Reaction of α‐Imino Esters with Alkenyl Halides

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(7)

Опубликована: Янв. 2, 2024

Chromium-catalyzed enantioselective Nozaki-Hiyama-Kishi (NHK) reaction represents one of the most powerful approaches for formation chiral carbon-heteroatom bond. However, construction sterically encumbered tetrasubstituted stereocenter through NHK still posts a significant challenge. Herein, we disclose cobalt-catalyzed aza-NHK ketimine with alkenyl halide to provide convenient synthetic approach manufacture enantioenriched α-vinylic amino acid. This protocol exhibits excellent functional group tolerance 99 % ee in cases. Additionally, this asymmetric reductive method is also applicable aldimine access trisubstituted stereogenic centers.

Язык: Английский

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Recent Advances in Asymmetric Organometallic Electrochemical Synthesis (AOES)

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 19, 2025

ConspectusIn recent years, our research group has dedicated significant effort to the field of asymmetric organometallic electrochemical synthesis (AOES), which integrates electrochemistry with transition metal catalysis. On one hand, we have rationalized that compounds can serve as molecular electrocatalysts (mediators) reduce overpotentials and enhance both reactivity selectivity reactions. other conditions for catalysis be substantially improved through electrochemistry, enabling precise modulation metal's oxidation state by controlling potentials regulating electron transfer rate via current adjustments. This synergistic approach addresses key challenges inherent in traditional catalysis, particularly those related use redox-active chemical reagents. Furthermore, redox conveniently tuned modifying their ligands, thereby governing reaction regioselectivity stereoselectivity. As a result, AOES emerged powerful promising tool chiral compounds.In this Account, summarize contextualize efforts AOES. Our primary strategy involves leveraging controllability potential regulate organometallics, facilitating desired An efficient platform was established under mild conditions, significantly reducing reliance on been systematically categorized into three sections based distinct electrolysis modes: combined anodic oxidation, cathodic reduction, paired electrolysis. In each section, highlight innovative discoveries tailored unique characteristics respective modes.In many transformations, metal-catalyzed reactions involving reagents utilizing exhibit similar reactivities. However, also observed notable differences certain cases. These findings include following: (1) Enhanced efficiency synthesis: instance, Rh-catalyzed enantioselective functionalization C–H bonds demonstrates superior efficiency. (2) Expanded scope transformations: previously challenging achieved due tunability potentials. A example is reductive coupling aryl chlorides, expands range accessible transformations. Additionally, mechanistic studies explore techniques intrinsic such controlled experiments, impact electrode materials catalyst performance, cyclic voltammetry studies. investigations provide more intuitive understanding behavior catalysts study mechanisms, guide design new catalytic systems.The advancements offer robust environmentally friendly sustainable selective By integrating developed versatile organic not only enhances but reduces environmental impact. We anticipate Account will stimulate further innovation realm AOES, leading discovery systems development synthetic methodologies.

Язык: Английский

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