Palladium‐Catalyzed Silylcyanation of Ynamides: Regio‐ and Stereoselective Access to Tetrasubstituted 3‐Silyl‐2‐Aminoacrylonitriles DOI Creative Commons

Pierre Hansjacob,

Frédéric R. Leroux, Vincent Gandon

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(14)

Published: Jan. 21, 2022

Abstract The palladium‐catalyzed silylcyanation of ynamides is described. This reaction fully regioselective, delivering tetrasubstituted 2‐aminoacrylonitriles derivatives exclusively. Unexpectedly, the nature (aryl or alkyl) substituent located at β‐position ynamide directly controls stereoselectivity. tolerates a number functional groups and can be considered as first general access to substituted 2‐aminoacrylonitriles. Given singular reactivity observed, computational study was performed shed light on mechanism this intriguing transformation. Relying specific newly installed vinylsilane functionality, scope has been enlarged by postfunctionalization.

Language: Английский

Metal-catalyzed Markovnikov-type selective hydrofunctionalization of terminal alkynes DOI
Jieping Chen, Wen‐Ting Wei, Zhuocheng Li

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(14), P. 7566 - 7589

Published: Jan. 1, 2024

Metal-catalyzed highly Markovnikov-type selective hydrofunctionalization of terminal alkynes provides a straightforward and atom-economical route to access 1,1-disubstituted alkenes, which have wide range applications in organic synthesis. However, the transformations are challenging due electronic steric effects during addition process. With development metal-catalyzed synthesis, different metal catalysts been developed solve this challenge, especially for platinum group catalysts. In perspective, we review homogeneous according classified element types as well reaction mechanisms. Future avenues investigation also presented help expand exciting field.

Language: Английский

Citations

19

Cobalt-Catalyzed C(sp2)–CN Bond Activation: Cross-Electrophile Coupling for Biaryl Formation and Mechanistic Insight DOI

Céline Dorval,

Maxime Tricoire,

Jeanne‐Marie Begouin

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(21), P. 12819 - 12827

Published: Oct. 19, 2020

Herein, we report a cross-electrophile coupling of benzonitrile derivatives and aryl halides with simple cobalt-based catalytic system under mild conditions to form biaryl compounds. Even though the cobalt catalyst is able activate C(sp2)–CN bond alone, use AlMe3 Lewis acid enhances reactivity benzonitriles improves cross-selectivity barely any influence on functional group compatibility. X-ray structure determination an original low-valent species combined stoichiometric reactions reveals catalytically active cobalt(I) toward halide partner. On other hand, experimental insights, including cyclic voltammetry experiments, suggest involvement complex lower oxidation state derivative. Finally, density theory calculations support proposed mechanistic cycle involving two different states perform reaction.

Language: Английский

Citations

61

Ligand‐Enabled Gold‐Catalyzed Cyanation of Organohalides DOI Open Access
Anil Kumar, Nandita Bhattacharya, Manoj V. Mane

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(47)

Published: Aug. 12, 2024

Abstract Herein, we disclose the first report on gold‐catalyzed C(sp 2 )‐CN cross‐coupling reaction by employing a ligand‐enabled Au(I)/Au(III) redox catalysis. This transformation utilizes acetone cyanohydrin as nucleophilic cyanide source to convert simple aryl and alkenyl iodides into corresponding nitriles. Combined experimental computational studies highlighted crucial role of cationic silver salts in activating stable (P,N)‐AuCN complex towards oxidative addition subsequently generate key aryl‐Au(III) complexes.

Language: Английский

Citations

9

Ligand-Controlled Ni-Catalyzed Regiodivergent Hydrocyanation of Unactivated Alkynes toward Linear and Branched Vinyl Nitriles DOI

Jiangkai Ma,

Anjiang Qiao,

Binglei Wang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2896 - 2903

Published: Feb. 3, 2025

Language: Английский

Citations

1

Palladium‐Catalyzed Silylcyanation of Ynamides: Regio‐ and Stereoselective Access to Tetrasubstituted 3‐Silyl‐2‐Aminoacrylonitriles DOI Creative Commons

Pierre Hansjacob,

Frédéric R. Leroux, Vincent Gandon

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(14)

Published: Jan. 21, 2022

The palladium-catalyzed silylcyanation of ynamides is described. This reaction fully regioselective, delivering tetrasubstituted 2-aminoacrylonitriles derivatives exclusively. Unexpectedly, the nature (aryl or alkyl) substituent located at β-position ynamide directly controls stereoselectivity. tolerates a number functional groups and can be considered as first general access to substituted 2-aminoacrylonitriles. Given singular reactivity observed, computational study was performed shed light on mechanism this intriguing transformation. Relying specific newly installed vinylsilane functionality, scope has been enlarged by postfunctionalization.

Language: Английский

Citations

21

The application and development of cyanating reagents in asymmetric cyanation reactions DOI
Ruirui Hua, Chukai Shao, Fu‐Xue Chen

et al.

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: unknown, P. 155549 - 155549

Published: March 1, 2025

Language: Английский

Citations

0

Regioselective Hydrocyanation of Internal Alkynes Enabled by a Transition‐Metal‐Free Dual‐Catalytic System DOI

Aleksandra Zasada,

Dawid Lichosyt

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: April 27, 2025

Abstract Since its discovery in 1954, the hydrocyanation of multiple carbon‐carbon bonds has emerged as a powerful strategy for synthesis nitriles. However, elusive control selectivity and typical reliance on expensive toxic transition metal (TM) based catalysts significantly hinder utility this process. Here, we report an exclusively regioselective unbiased alkynes, driven by base‐catalyzed reversible alkyne‐allene isomerization phosphine‐catalyzed HCN transfer to allene. This TM‐free, dual‐catalytic approach introduces novel mode via allene intermediate. The methodology secures cost‐effective access broad range vinyl nitriles (40 examples) with yields up 97% Z/E stereoselectivity 20:1, including complex natural product derivatives. A comparison TM‐based systems highlighted 2500‐fold cost reduction, well elimination troublesome separation regioisomers. Mechanistic studies elucidated reaction pathway, shedding light achieved regioselectivity. By altering one catalyst system, demonstrated regioselectivity switch, thereby facilitating regiodivergent (eight examples). In broader context, offers foundation developing next generation TM‐free strategies hydrofunctionalizations alkynes.

Language: Английский

Citations

0

TBACN-Promoted Regioselective Cyanofunctionalization and Benzannulation: Enabling Access to Cyanoindolizine Scaffolds via Alkyne Cyclization DOI Creative Commons

Sergen Gül,

Karina Amudi, Burak Kuzu

et al.

ACS Omega, Journal Year: 2025, Volume and Issue: unknown

Published: May 5, 2025

A novel and regioselective cyanofunctionalization-benzannulation cascade reaction has been developed, utilizing tetrabutylammonium cyanide (TBACN) as a practical efficient source. This transformation provides streamlined access to structurally diverse array of cyano-substituted indolizine scaffolds, which are valuable intermediates in the synthesis nitrogen-containing heterocycles with potential pharmaceutical applications. The methodology employs readily available N-propargyl pyrrole derivatives starting materials proceeds under relatively mild conditions, enabling 20 distinct cyanoindolizine derivatives. exhibits remarkable regioselectivity installation cyano group, feature that was not initially anticipated. unexpected outcome elucidated through combination control experiments, by-product analysis, intermediate isolation, shedding light on underlying mechanistic pathway. Furthermore, displays broad substrate scope, demonstrating high functional group tolerance respect both electronic steric variations ring propargyl substituents. versatility is further highlighted by for downstream transformations into other groups, such amide moieties, expand synthetic utility obtained scaffolds. Importantly, this work represents first reported example TBACN-mediated benzannulation units, marking significant advancement field heterocyclic chemistry. strategy only route complex frameworks but also offers insights opportunities design development biologically relevant heterocycles.

Language: Английский

Citations

0

Iron-catalyzed formation of six-membered rings from alkyne DOI Creative Commons
Hui Li,

Sang I. Yi,

Chunling Zeng

et al.

Green Synthesis and Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: May 1, 2025

Language: Английский

Citations

0

Synthesis of 3-thiocyanated chromones via TCCA/NH4SCN-mediated cyclization/thiocyanation of alkynyl aryl ketones DOI Creative Commons
Jiaxi Xiao, Zhenkang Ai, Xuemin Li

et al.

Green Synthesis and Catalysis, Journal Year: 2021, Volume and Issue: 3(2), P. 198 - 201

Published: Dec. 24, 2021

3-Thiocyanated chromones was conveniently synthesized from alkynyl aryl ketones using commercially available, inexpensive trichloroisocyanuric acid (TCCA) as oxidant and NH4SCN thiocyanato (SCN) source. This metal-free approach is postulated to first in situ generate thiocyanogen chloride (Cl-SCN) the reaction of TCCA NH4SCN, followed by a rare efficient electrophilic thiocyano oxyfunctionalization alkynes enabled reactive species generated thereof.

Language: Английский

Citations

15