Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO₂

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2919 - 2927

Published: Jan. 26, 2024

Dicarboxylic acids and derivatives are important building blocks in organic synthesis, biochemistry, the polymer industry. Although catalytic dicarboxylation with CO2 represents a straightforward sustainable route to dicarboxylic acids, it is still highly challenging limited generation of achiral or racemic acids. To date, asymmetric give chiral has not been reported. Herein, we report first 1,3-dienes via Cu catalysis. This strategy provides an efficient environmentally benign high regio-, chemo-, enantioselectivities. The copper self-relay catalysis, that is, Cu-catalyzed boracarboxylation carboxylated allyl boronic ester intermediates subsequent carboxylation C–B bonds dicarboxylates, key success this dicarboxylation. Moreover, protocol exhibits broad substrate scope, good functional group tolerance, easy product derivatizations, facile synthesis liquid crystalline polyester drug-like scaffolds.

Language: Английский

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Catalytic Regio- and Enantioselective Boracarboxylation of Arylalkenes with CO₂ and Diboron

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2888 - 2894

Published: Jan. 26, 2024

Catalytic asymmetric carboxylation of readily available alkenes with CO2, an abundant and sustainable one-carbon building block, that gives access to value-added α-stereogenic carboxylic acids in atom- step-economic manner is highly attractive. However, it has remained a formidable challenge for the synthetic community. Here, first example Cu-catalyzed regio- enantioselective boracarboxylation reaction on various arylalkenes diboron under atmospheric pressure CO2 described, which afforded variety chiral β-boron-functionalized α-aryl up 87% yield 97% ee mild conditions. Importantly, α-substituted could also be subject this protocol excellent enantiopurities, thereby rendering efficient approach generation enantioenriched α-chiral all-carbon quaternary center. Moreover, high functional group tolerance, scalable synthesis, facile bioactive compounds, like (−)-scopolamine, (−)-anisodamine, (−)-tropicamide, further demonstrated utility strategy.

Language: Английский

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Enantioselective Nickel-Electrocatalyzed Reductive Propargylic Carboxylation with CO₂

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(21), P. 14864 - 14874

Published: May 16, 2024

The exploitation of carbon dioxide (CO2) as a sustainable, plentiful, and harmless C1 source for the catalytic synthesis enantioenriched carboxylic acids has long been acknowledged pivotal task in synthetic chemistry. Herein, we present current-driven nickel-catalyzed reductive carboxylation reaction with CO2 fixation, facilitating formation C(sp3)–C(sp2) bonds by circumventing handling moisture-sensitive organometallic reagents. This electroreductive protocol serves practical platform, paving way propargylic (up to 98% enantiomeric excess) from racemic carbonates CO2. efficacy this transformation is exemplified its successful utilization asymmetric total (S)-arundic acid, (R)-PIA, (S)-chizhine D, (S)-cochlearin G, (S,S)-alexidine, thereby underscoring potential electrosynthesis achieve complex molecular architectures sustainably.

Language: Английский

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Kinetically-Controlled Ni-Catalyzed Direct Carboxylation of Unactivated Secondary Alkyl Bromides without Chain Walking

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 1753 - 1759

Published: Jan. 9, 2024

Herein, we report the direct carboxylation of unactivated secondary alkyl bromides enabled by merger photoredox and nickel catalysis, a previously inaccessible endeavor in arena. Site-selectivity is dictated kinetically controlled insertion CO2 at initial C(sp3)–Br site rapid formation Ni(I)–alkyl species, thus avoiding undesired β-hydride elimination chain-walking processes. Preliminary mechanistic experiments reveal subtleties stereoelectronic effects for guiding reactivity site-selectivity.

Language: Английский

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Recent Advances in Asymmetric Organometallic Electrochemical Synthesis (AOES)

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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Atropisomeric Carboxylic Acids Synthesis via Nickel‐Catalyzed Enantioconvergent Carboxylation of Aza‐Biaryl Triflates with CO₂

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: March 26, 2024

Abstract Upgrading CO 2 to value‐added chiral molecules via catalytic asymmetric C−C bond formation is a highly important yet challenging task. Although great progress on the of centrally carboxylic acids has been achieved, construction axially with never reported date. Herein, we report first synthesis , which enabled by nickel‐catalyzed dynamic kinetic reductive carboxylation racemic aza‐biaryl triflates. A variety acids, are valuable but difficult obtain catalysis, generated in an enantioconvergent version. This new methodology features good functional group tolerance, easy scale‐up, facile transformation and avoids cumbersome steps, handling organometallic reagents using stoichiometric materials. Mechanistic investigations indicate process induced nickel catalysis.

Language: Английский

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Advancing Heterogeneous Organic Synthesis With Coordination Chemistry‐Empowered Single‐Atom Catalysts

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 18, 2024

Abstract For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of active centers. Comparatively, preparation single‐atom catalysts much easier with more straightforward effective accesses arrangement control The presence coordination atoms or neighboring functional on supports' surface ensures stability single‐atoms their interactions individual substantially regulate performance Therefore, collaborative interaction between surrounding environment enhances initiation reaction substrates formation transformation crucial intermediate compounds, which imparts significant catalytic efficacy, rendering them a valuable framework investigating correlation structure activity, as well mechanism in organic reactions. Herein, comprehensive overviews both homogeneous complexes reactions are provided. Additionally, reflective conjectures about advancement synthesis also proposed present reference later development.

Language: Английский

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Design and Application of New Pyridine-Derived Chiral Ligands in Asymmetric Catalysis

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(6), P. 957 - 970

Published: March 6, 2024

ConspectusThe innovation of chiral ligands has been crucial for the asymmetric synthesis functional molecules, as demonstrated by several types widely applied "privileged" ligands. In this context, pyridine-derived ligands, far some oldest and most utilized in catalysis, have attracted considerable research interest past half-century. However, development broadly applicable pyridine units (CPUs) plagued intertwining challenges, thus delaying advancements many reactions.This Account aims to summarize recent progress new CPU-containing focusing on a rationally designed, modular, tunable CPU developed our laboratory. A significant problem thwarting conventional designs is paradox between broad reactivity stereoselectivity; that is, while enhanced stereoselectivity may be achieved introducing elements close N atom, concomitant increase local steric hindrance often limits catalytic activity scope. Our newly features rigid [6-5-3] fused-ring framework spirocyclic ketal side wall. The well-defined three-dimensional structure minimizes (inner layer) tunes peripheral environment (outer remote substituents, securing stereoselectivity. Different chelating were readily assembled using structural module, with applications mechanistically diverse transition-metal-catalyzed reactions. Thus, series 2,2′-bipyridine successfully employed general, efficient, highly enantioselective nickel-catalyzed intermolecular reductive addition, Ullmann coupling ortho-chlorinated aryl aldehydes, carboxylation benzylic (pseudo)halides CO2. Notably, these exhibited superior reactions compared common N-based iridium-catalyzed C–H borylation was N,B-bidentate ligand. Furthermore, challenging, additive-free, broad-scope transfer hydrogenative direct amination half-sandwich iridium catalyst supported N,C-bidentate excellent performance high stereoselectivity, which, when combined experimental computational mechanistic investigations, "double-layer control" design concept.Considering described herein should inspire creation novel catalysts drive

Language: Английский

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2,2′‐Thienoviologens with Low Reduction Potential for Electrochromism and Visible‐Light‐Driven Hydrogen Evolution Using g‐C₃N₄‐Based Composites via Hydrogen Bonds

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(26)

Published: May 8, 2024

Abstract A series of sulfur‐bridged 2,2′‐viologens, 2,2′‐thienoviologens (2,2′‐SV 2+ ) with propyl bridge and hydroxyl bridges, are synthesized for the first time. The exhibited improved visible‐light absorption, narrow energy gap, more negative reduction potential (160 mV lower than 4,4′‐thienoviologens) stable free radical states compared 4,4′‐thienoviologens parent 2,2′‐viologens. utilization femtosecond transient absorption (fs‐TA) demonstrated that 2,2′‐thienoviologen can produce distinct charge‐separated under visible light excitation. Due to their excellent photophysical electrochemical properties, used electrochromic devices combined g‐C 3 N 4 via hydrogen bonds catalytic production. Based on advantageous electron‐donating properties 2,2′‐SV , release efficiency 2,2′‐thienoviologens‐modified composites is 8542 µmol·h −1 ·g a value highest reported production from organic small‐molecule‐modified 78 times higher unmodified . This study presents concise method convert solar broaden applications 2,2′‐viologens in photocatalytic systems.

Language: Английский

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Synergistic Photoredox/Palladium Catalyzed Enantioconvergent Carboxylation of Racemic Heterobiaryl (Pseudo)Halides with CO₂

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Aug. 16, 2024

Herein, we report a synergistic photoredox/palladium catalytic system for the efficient enantioconvergent synthesis of axially chiral esters from racemic heterobiaryl (pseudo)halides (bromides/triflates) with CO

Language: Английский

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