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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Switchable divergent di- or tricarboxylation of allylic alcohols with CO2

Chem, Journal Year: 2024, Volume and Issue: 10(3), P. 938 - 951

Published: Jan. 10, 2024

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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Synergistic Effects of Co–Fe Boosts the Transformation of CO₂ into C₆₊ Dicarboxylic Acids up to Gram-Scale under Mild Conditions

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1459 - 1467

Published: Jan. 13, 2024

Electrochemical carboxylation of 1,3-dienes with carbon dioxide (CO2) is a feasible method to obtain dicarboxylic derivatives, which are important synthetic intermediates polymers and pharmaceuticals. However, due unavoidable byproducts unfriendly conditions, the formation pure acids has been limited. In this work, we report that bimetallic phosphating CoFeP catalyst on nickel foam (CoFeP/NF) served as remarkable electrode, transforms CO2 into multicarbon (C6+) acids. The synergistic effects between Co Fe allow activation mainly, in electron transfer easier proceeded afford radical anion diene, pursuant further formed ultimate carboxylated products. reaction can occur commercial flow cell gram-scale amplification. acid obtained was up 1.08 g at 5 mmol scale 1,3-dienes, illustrating high electrocatalytic activity practical application CoFeP/NF.

Language: Английский

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Photochemical Reductive Carboxylation of N-Benzoyl Imines with Oxalate Accelerated by Formation of EDA Complexes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(13), P. 10053 - 10059

Published: June 20, 2024

Language: Английский

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Metallaphotoredox-catalyzed alkynylcarboxylation of alkenes with CO2 and alkynes for expedient access to β-alkynyl acids

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 21, 2025

Carboxylation with CO2 offers an attractive and sustainable access to valuable carboxylic acids. Among these methods, direct C−H carboxylation of terminal alkynes has attracted much attention for one-carbon homologation alkynes, enabling rapid synthesis propiolic In contrast, the multi-carbons construct important non-conjugated alkynyl-containing acids not been reported. Herein, we present alkynylcarboxylation alkenes via photoredox copper dual catalysis. This protocol provides a practical method form alkynyl from readily available CO2. Additionally, this approach also features mild (room temperature, 1 atm CO2) redox-neutral conditions, high atom step economy, good functional group tolerance, selectivities. Moreover, diverse transformations β-alkynyl acid products bioactive molecule (GPR40/FFA1 agonist) further illustrate synthetic utility methodology. The report multi-carbon is rare. authors catalysis, affording

Language: Английский

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C(sp³)–H Carboxylation via Carbene/Photoredox Cooperative Catalysis

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(2), P. 1287 - 1293

Published: Jan. 7, 2025

C(sp3)–H bond functionalization is a powerful strategy for the synthesis of organic compounds due their abundance in simple starting materials. Photoredox catalysis has led to diverse array enabling activation strategies; however, general platform direct carboxylic acid derivatives remains elusive. Disclosed herein development cooperative NHC/photoredox-catalyzed esterification transformation. This method enables access benzylic, α-heteroatom, and formal β-esterification products moderate high yields under mild reaction conditions.

Language: Английский

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Electro-reductive carboxylation of C Cl bonds in unactivated alkyl chlorides and polyvinyl chloride with CO2

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(12), P. 110104 - 110104

Published: June 8, 2024

Language: Английский

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Electroreductive Cross-Coupling Reactions: Carboxylation, Deuteration, and Alkylation

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

ConspectusElectrochemistry has been used as a tool to drive chemical reactions for more than two centuries. With the help of an electrode and power source, chemists are provided with system whose potential can be precisely dialed in. The theoretically infinite redox range renders electrochemistry capable oxidizing or reducing some most tenacious compounds. Indeed, electroreduction offers alternative generating highly active intermediates from electrophiles (e.g., halides, alkenes, etc.) in organic synthesis, which untouchable traditional reduction methods. Meanwhile, reductive coupling extensively utilized both industrial academic settings due their ability swiftly, accurately, effectively construct C–C C–X bonds, present innovative approaches synthesizing complex molecules. Nonetheless, its application is constrained by several inherent limitations: (a) requirement stoichiometric quantities agents, (b) scarce activation strategies inert substrates high potentials, (c) incomplete mechanistic elucidation, (d) challenges isolation intermediates. merging represents attractive approach address above limitations synthesis seen increasing use synthetic community over past few years.Since 2020, our group dedicated developing electroreductive cross-coupling using readily available small molecules, such arenes, CO2, D2O, value-added products. Electroreductive chemistry versatile powerful capacity precise selectivity control, allowed us develop three electrochemical modes lab: (1) An economically advantageous direct (EDR) strategy that emphasizes efficiency, achieves atom utilization, minimizes unnecessary atomic waste. (2) A class organo-mediated (EOMR) methods controlling reaction pathways. This allows modulation processes enhance efficiency selectivity. (3) metal-catalyzed (EMCR) method enables selective functionalization specific bonds functional groups under mild conditions, thereby occurrence side reactions. We commenced studies establishing organic-mediator-promoted carboxylation aryl alkyl halides. was then employed arylcarboxylation simple styrenes halides manner. electrolysis arenes epoxides CO2 carboxyl source achieved. Moreover, through adjustment we successfully accomplished deuteration olefins, unactivated enabling efficient formation D-labeled Finally, building on previous understanding developed series alkylation enable C(sp3)–C(sp3)

Language: Английский

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Arenethiolate-Catalyzed 1,5-HAT of Aryl Halides: Synthesis of γ-Spirolactams

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3081 - 3085

Published: April 3, 2024

γ-Spirolactam is a privileged building block that found in wide range of natural products and bioactive compounds. Herein, we report an arenethiolate-catalyzed 1,5-HAT aryl halides to obtain γ-spirolactams through SET reduction/intramolecular 1,5-HAT/cyclization/HAT process. This protocol features metal-free conditions broad substrate scope, furnishing the moderate excellent yields. Notably, bromides, chlorides even fluorides are well tolerated this transformation. A mechanism involving arenethiolate as catalyst proposed based on DFT calculation.

Language: Английский

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