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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Copper-Catalyzed Regiodivergent and Enantioselective Hydrosilylation of Allenes

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(12), P. 5535 - 5542

Published: March 17, 2022

A copper-catalyzed regiodivergent hydrosilylation of a wide range simple allenes is reported. Linear and branched allylsilanes were formed by judicious choice solvents. Furthermore, obtained with high enantioselectivity (up to 97% enantiomeric excess) the aid C2-symmetric bisphosphine ligand in unprecedented asymmetric allene hydrosilylation.

Language: Английский

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Confronting the Challenging Asymmetric Carbonyl 1,2-Addition Using Vinyl Heteroarene Pronucleophiles: Ligand-Controlled Regiodivergent Processes through a Dearomatized Allyl–Cu Species

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(13), P. 5985 - 5995

Published: March 26, 2022

The selective reductive coupling of vinyl heteroarenes with aldehydes and ketones represents a versatile approach for the rapid construction enantiomerically enriched secondary tertiary alcohols, respectively. Herein, we demonstrate CuH-catalyzed regiodivergent carbonyl-containing electrophiles, in which selectivity is controlled by ancillary ligand. This leverages an situ generated benzyl- or dearomatized allyl-Cu intermediate, yielding either exocyclic addition products, method exhibits excellent regio-, diastereo-, enantioselectivity tolerates range common functional groups heterocycles. dearomative pathway allows direct access to variety functionalized saturated heterocyclic structures. reaction mechanism was probed using combination experimental computational approach. Density theory studies suggest that ligand-controlled regioselectivity results from C-H/π interaction steric repulsion transition states, leading major minor regioisomers, Hydrocupration heteroarene pronucleophile enantiodetermining step, whereas diastereoselectivity enforced interactions between benzylic intermediate substrates six-membered cyclic state.

Language: Английский

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Dearomative Addition-Hydrogen Autotransfer for Branch-Selective N-Heteroaryl C–H Functionalization via Ruthenium-Catalyzed C–C Couplings of Diene Pronucleophiles

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 6, 2025

A novel mechanism for N-heteroaryl C–H functionalization via dearomative addition-hydrogen autotransfer is described. Upon exposure to the catalyst derived from RuHCl(CO)(PPh3)3 and Xantphos, dienes 1a–1g suffer hydroruthenation form allylruthenium nucleophiles that engage in addition-β-hydride elimination furnish branched products of C–C coupling 3a–3s 4a–4f. Oxidative cleavage isoprene adducts 3j, 3k, 3l, 3n followed by ruthenium-catalyzed dynamic kinetic asymmetric ketone reduction provides enantiomerically enriched N-heteroarylethyl alcohols 6a–6d and, therefrom, amines 7a–7d. Density functional theory calculations correlate experimentally observed regioselectivities with magnitude LUMO coefficients corroborate rate-determining addition. In presence 2-propanol trifluoroethanol, dearomatized pyrimidine 2a quinazoline 2n were isolated characterized.

Language: Английский

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Recent Advances in Catalytic Asymmetric Ketone Allylations and Their Applications

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1487 - 1513

Published: Jan. 9, 2025

Due to the wide applications of resulting chiral tertiary homoallylic alcohols in organic synthesis, catalytic asymmetric ketone allylations have attracted continuous attention from synthetic chemists. Despite inherent difficulty enantiofacial differentiation and low reactivity ketones, past two decades witnessed rapid progress allylation ketones. Many efficient methods been reported, with discovery unprecedented catalysts reagents. The current Review aims give a summary achievements this area 2011 date is divided into six parts according reagents that were applied. Special paid scope application each method brief introduction corresponding mechanisms.

Language: Английский

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Dual Cobalt/Organophotoredox Catalysis for Diastereo- and Regioselective 1,2-Difunctionalization of 1,3-Diene Surrogates Creating Quaternary Carbon Centers

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(6), P. 3651 - 3659

Published: March 7, 2022

The synthesis of compounds having quaternary carbon centers through a catalytic stereo- and regioselective difunctionalization 2-substituted 1,3-dienes remains elusive. Here, we present dual Co/photoredox-catalyzed cascade approach that addresses this challenge using modular vinyl cyclic carbonates functioning as masked 2-aryl-1,3-diene surrogates. latter species are conveniently prepared in situ converted into nucleophilic Co(allyl) intermediates intercepted by aldehydes to afford homoallylic alcohols with ample scope reaction partners. developed protocol marks significant step forward the use structurally versatile their 1,2-hydroalkylation 1,2-dicarbofunctionalization.

Language: Английский

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Organophotoredox/Ni-Cocatalyzed Allylation of Allenes: Regio- and Diastereoselective Access to Homoallylic Alcohols

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(5), P. 3249 - 3255

Published: Feb. 24, 2022

A dual organophotoredox/nickel-catalyzed reductive coupling of allenes with aldehydes has been developed for the rapid assembly anti-homoallylic alcohols high levels regioselectivities (>20:1), diastereoselectivities (up to >20:1), and yields 91%). The allylation was realized through a crucial π-allylnickel intermediate, which obtained via insertion Ni–H intermediate. Moreover, γ,γ-disubstituted homoallylic quaternary stereocenter can also be prepared by this protocol.

Language: Английский

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Cobalt‐Catalyzed Regiodivergent and Enantioselective Intermolecular Coupling of 1,1‐Disubstituted Allenes and Aldehydes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(19)

Published: March 3, 2023

Catalytic enantioselective coupling of 1,1-disubstituted allenes and aldehydes through regiodivergent oxidative cyclization followed by stereoselective protonation or reductive elimination promoted chiral phosphine-Co complexes is presented. Such processes represent unprecedented unique reaction pathways for Co catalysis that enable catalytic generation metallacycles with divergent regioselectivity accurately controlled ligands, affording a wide range allylic alcohols homoallylic are otherwise difficult to access without the need pre-formation stoichiometric amounts alkenyl- allyl-metal reagents in up 92 % yield, >98 : 2 regioselectivity, dr >99.5 0.5 er.

Language: Английский

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Dual‐Catalysed Intermolecular Reductive Coupling of Dienes and Ketones**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(2)

Published: Nov. 10, 2023

Abstract We report a mild, catalytic method for the intermolecular reductive coupling of feedstock dienes and styrenes with ketones. Our conditions allow concomitant formation cobalt hydride species single‐electron reduction Subsequent selective hydrogen‐atom transfer from generates an allylic radical which can selectively couple persistent radical‐anion ketone. This radical‐radical negates unfavourable steric interactions ionic pathways avoids unstable alkoxy previous olefin‐carbonyl couplings, were limited, as result, to aldehydes. Applications this novel straightforward approach include efficient synthesis drug molecules, key intermediates in site‐selective late‐stage functionalisation.

Language: Английский

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Regiodivergent and Stereoselective Synthesis of Highly Substituted 1,3-Dienes via Arylative Acyloxy Migration of Propargyl Esters

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(32), P. 18115 - 18125

Published: Aug. 1, 2023

We report the first catalyst-controlled regiodivergent method that enables synthesis of structurally diverse 1,2,3,4-tetrasubstituted conjugated dienes with excellent regio- and stereochemical outcomes from same set readily available propargyl esters diaryliodonium salts. In this diene chemistry, in situ generated, highly electrophilic aryl-CuIII complex serves not only as a π-Lewis acid catalyst for alkyne activation/acyloxy migration but also an aryl electrophile equivalent. The competitive arylative 1,2- 1,3-acyloxy patterns are exquisitely dictated by Cu Au/Cu relay catalyses, respectively, providing modular attractive approach to traditionally inaccessible tetrasubstituted 1,3-dienes manner. Finally, synthetic utility is demonstrated further derivatization into array useful compounds.

Language: Английский

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