Cited by Site‐Selective Activation and Stereospecific Functionalization of Bis(boronic esters) Derived from 2‐Alkenes: Construction of Propionates and Other 1,2‐Difunctional Motifs

Photoredox/Cr-catalyzed enantioselective radical-polar crossover transformation via C-H functionalization DOI

Siyuan Tang,

Z. Z. Wang,

Ao Yu

et al.

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

Published: Feb. 4, 2025

Asymmetric multicomponent reactions that aim to control multiple chiral centers with high selectivity in a single step remain an on-gonging challenge. The realm of enantioselective radical-polar crossover transformation achieved through C-H Functionalization has yet be fully explored. Herein, we present successful description photoredox/Cr-catalyzed three-component (hetero)arylalkylation 1,3-dienes functionalization. A diverse array homoallylic alcohols could obtained good excellent yields, accompanied by outstanding enantioselectivity. asymmetric build two simultaneously and demonstrates broad substrate tolerance, accommodating various drug-derived aldehydes, (hetero)aromatics, 1,3-diene derivatives. Preliminary mechanistic studies indicate the involvement radical intermediate, allylic chromium species reacting aliphatic aromatic aldehydes Zimmerman–Traxler transition states enabled dual photoredox catalysis. ongoing Here, authors photoredox- chromium-catalyzed

Language: Английский

Citations

Enantioselective Directed Nickel-Catalyzed Three-Component Reductive Arylalkylation of Alkenes via the Carbometalation/Radical Cross-Coupling Sequence DOI

Zhan Dong,

Changyu Xu,

Jianchao Chang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4395 - 4406

Published: March 8, 2024

Asymmetric reductive three-component arylalkylation of alkenes via the radical relay method has been well established, while asymmetric migratory insertion strategy remains unexplored. We report enantioselective nickel-catalyzed cross-electrophile with aryl- and alkyl halides an integrated Heck carbometalation/radical cross-coupling sequence. This protocol employing a chiral Ni/PHOX catalytic system allows terminal internal to successfully engage exquisite control regio-, chemo-, stereoselectivity. More importantly, this undergoes regio- arylnickelation followed by Csp3–Csp3 elimination, thus exhibiting reverse regioselectivity method. Mild reaction conditions exceptional functional group tolerance facilitate method's compatibility bioactive motifs modular synthesis biologically active compounds. The experiments density theory calculations provide insights into mechanism origin stereoselectivity, hemilabile nature PHOX ligand is critical for achieving arylalkylation.

Language: Английский

Citations

Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins DOI

Wenyi Huang,

Yang Xi,

Deng Pan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16892 - 16901

Published: June 6, 2024

The development of a catalytic method for stereogenic carbon center formation holds immense significance in organic synthesis. Transition-metal-catalyzed cross-coupling reaction has been regarded as straightforward and efficient tool stereoselectively forging C–C bond. Nevertheless, the creation acyclic all-carbon quaternary-containing vicinal stereocenters remains notoriously challenging within domain chemistry despite their prominence various bioactive small molecules. Herein, we describe palladium-catalyzed asymmetric multicomponent trisubstituted alkene with aryl diazonium salts arylboronic acids to realize tertiary-quaternary centers high regio-, distereo-, enantioselectivity. Specifically, precise manipulation stereoconfiguration alkenes enables divergent stereoselective reaction, thus allowing facile construction all four enantiomers. Harnessing ligand-swap strategy involving chiral bisoxazoline an achiral fumarate individually accelerates enantioselective migratory insertion reductive elimination step process, supported by density functional theory (DFT) calculations, obviating requirement neighboring directing group internal olefin skeleton.

Language: Английский

Citations

Copper-Catalyzed Enantioselective Three-Component Fluoroalkylalkynylation of Unactivated Alkenes DOI

Mengxia Liao,

Cuihuan Geng,

Zhiguo Wu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1693 - 1703

Published: Jan. 16, 2025

The enantioselective three-component dicarbonfunctionalization of electronically unactivated alkenes continues to pose a significant challenge. In this work, copper-catalyzed highly regio- and fluoroalkylalkynylation with diverse terminal alkynes fluoroalkyl halides under mild conditions is developed. addition halides, Togni's reagent can also participate in the reaction, delivering chiral β-trifluoromethyl high enantioselectivities. This method exhibits good functional group tolerance, facilitating late-stage derivatization variety biologically active molecules. success chemistry was achieved by using bulky indene-substituted BOPA ligand. DFT calculations indicate that radical through fluorine-directed outer-sphere pathway. Mechanistic studies reveal amide crucial for achieving stereoselectivities because exclusive F···H hydrogen bonding between Mes on be formed stabilize Si-radical coupling transition state.

Language: Английский

Citations

Nickel‐Catalyzed Asymmetric Reductive 1,4‐ and 1,5‐Dicarbofunctionalization^† DOI

Yutong Xiang,

Chang Zhang,

Chuan Wang

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 8, 2025

Comprehensive Summary Herein, we present the first examples of asymmetric reductive 1,4‐dicarbofunctionalization 1,3‐dienes and 1,5‐dicarbofunctionalization vinylcyclopropanes, which proceed under catalysis a chiral nickel/bis‐imidazoline complex using alkyl halides aryl iodides or alkenyl bromides as electrophilic coupling partners. In these highly enantioselective transformations operating in radical relay mechanism, C(sp 3 )‐ 2 )‐type carbo‐moieties are respectively installed on terminal internal position with newly formed olefinic unit high E ‐selectivity.

Language: Английский

Citations

Nickel-Catalyzed Enantioselective Three-Component 1,2-Alkylarylation of Alkenes with Arylboronic Acids as Arylation Reagents DOI

Zhaodong Zhu, Jingjing Wu

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7833 - 7841

Published: April 25, 2025

Language: Английский

Citations

Triple cross-electrophile coupling enabled by palladium/norbornene cooperative catalysis DOI

Jinxiang Ye, Liang Qi, Shuang Deng

et al.

Science Advances, Journal Year: 2025, Volume and Issue: 11(18)

Published: May 1, 2025

Cross-electrophile coupling (XEC) is a powerful strategy for forming C–C bonds in synthetic organic chemistry. While XEC reactions between two electrophiles are well established, those involving three distinct have remained underdeveloped. Herein, we report an intriguing formal triple enabled by palladium/norbornene cooperative catalysis. Readily available aryl iodides, alkyl/aryl bromides, and propargyl esters used as the electrophilic partners, leading to synthesis of diverse array tetrasubstituted allenes. In particular, challenging asymmetric has also been realized through palladium/chiral norbornene catalysis, which uses sterically hindered 2,6-disubstituted bromides arylating reagents prepare allenes bearing axially chiral biaryl unit. Density functional theory calculations reveal that selection terminating key success this reaction because it enables thermodynamically favored pathway termination alkyne insertion followed β-O elimination.

Language: Английский

Citations

Transition metal-free decarboxylative olefination of carboxylic acid salts DOI

Ebbin Joseph, Deshkanwar Brar,

Gaven Stuhlsatz

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(24), P. 9353 - 9360

Published: Jan. 1, 2024

An expedient synthesis of electron-deficient styrenes is accomplished through decarboxylation and oxidation via halogen ion transfer. The resulting umpoled intermediates undergo a rebound elimination to furnish olefins.

Language: Английский

Citations

Metallaphotoredox-Catalyzed Three-Component Asymmetric Cross-Electrophile Coupling for Chiral Boronate Synthesis DOI

Xiaofang Li, Yuntong Hu,

Zhonghou Huang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(20), P. 15790 - 15798

Published: Oct. 10, 2024

Here, we report a photoredox and nickel-catalyzed cross-electrophile coupling strategy for the asymmetric three-component 1,2-alkylarylation of vinyl boronates with (hetero)aryl bromides (2°, 3°)-alkyl redox-active esters in presence Hantzsch ester. With fluorinated pyridyl-substituted chiral biimidazoline ligand, this reaction enables straightforward access to wide variety synthetically valuable α-aryl from readily available starting materials. This features mild conditions, broad substrate generality, good functional group tolerance proceeds without using metal reductants or alkyl halides. Furthermore, alkenyl halides other electron-deficient alkenes such as acrylates phosphonates can be applied successfully. Preliminary mechanistic studies shed light on potential pathways roles organic amines.

Language: Английский

Citations

Site‐Selective Activation and Stereospecific Functionalization of Bis(boronic esters) Derived from 2‐Alkenes: Construction of Propionates and Other 1,2‐Difunctional Motifs DOI

James P. Morken, Ningxin Xu, John L. Holmgren

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 13, 2024

Non-directed regioselective activation of bis(boronic esters), followed by functionalization, is reported. A bulky activator shown to selectively activate the less hindered boronic ester enabling it undergo stereospecific cross-coupling a variety electrophiles. This steric-based regioselectivity provides simple and efficient method prepare highly functionalized, enantiomerically enriched products starting from alkenes.

Language: Английский

Citations