Nickel‐Catalyzed Regio‐ and Enantioselective Migratory Hydrocyanation of Internal Alkenes: Expanding the Scope to α,ω‐Diaryl Internal Alkenes DOI

Mingdong Jiao,

Jinguo Long,

Jianxi Chen

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(21)

Published: March 25, 2024

Abstract Metal‐hydride‐catalyzed migratory functionalization of alkenes witnessed extensive development in the past few years. However, asymmetric version this reaction has remained largely underdeveloped owing to difficulty simultaneous control both regio‐ and stereoselectivity. In addition, exploring wider alkene substrate scope enable more synthetically valuable applications represents another challenge field. context, a nickel‐catalyzed hydrocyanation internal involving chain‐walking process is demonstrated. The exhibits excellent enantioselectivity, proceeds under mild conditions, delivers benzylic nitriles high yields. Even α,ω‐diaryl alkenes, which are known be one most challenging substrates type, could successfully converted desired products with good stereoselectivity by modifying electronic steric effects. Theoretical calculations suggest that η 3 ‐benzyl coordination mode aryl substituent (3,5‐(OMe) 2 C 6 H ) on diphosphite ligand key factors regulating enantioselectivity.

Language: Английский

Nickel‐Catalyzed Regio‐ and Enantioselective Migratory Hydrocyanation of Internal Alkenes: Expanding the Scope to α,ω‐Diaryl Internal Alkenes DOI

Mingdong Jiao,

Jinguo Long,

Jianxi Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 25, 2024

Abstract Metal‐hydride‐catalyzed migratory functionalization of alkenes witnessed extensive development in the past few years. However, asymmetric version this reaction has remained largely underdeveloped owing to difficulty simultaneous control both regio‐ and stereoselectivity. In addition, exploring wider alkene substrate scope enable more synthetically valuable applications represents another challenge field. context, a nickel‐catalyzed hydrocyanation internal involving chain‐walking process is demonstrated. The exhibits excellent enantioselectivity, proceeds under mild conditions, delivers benzylic nitriles high yields. Even α,ω‐diaryl alkenes, which are known be one most challenging substrates type, could successfully converted desired products with good stereoselectivity by modifying electronic steric effects. Theoretical calculations suggest that η 3 ‐benzyl coordination mode aryl substituent (3,5‐(OMe) 2 C 6 H ) on diphosphite ligand key factors regulating enantioselectivity.

Language: Английский

Citations

4
CoH-catalyzed asymmetric remote hydroalkylation of heterocyclic alkenes: a rapid approach to chiral five-membered S- and O-heterocycles DOI Creative Commons
Lingzi Zhao,

Feipeng Liu,

Yan Zhuang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(23), P. 8888 - 8895

Published: Jan. 1, 2024

A highly efficient method achieves precise construction of alkyl chiral centers at remote C3-positions in five-membered S/O-heterocycles via cobalt-catalyzed asymmetric hydroalkylation heterocyclic alkenes.

Language: Английский

Citations

4
Regio- and Enantioselective Hydromethylation of 3-Pyrrolines and Glycals Enabled by Cobalt Catalysis DOI Creative Commons

Mengyang Shen,

C. NIU,

Xuchao Wang

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(6), P. 2312 - 2322

Published: June 11, 2024

Enantioenriched 3-methylpyrrolidine, with its unique chiral nitrogen-containing core skeleton, exists widely in various functional molecules, including natural products, bioactive compounds, and pharmaceuticals. Traditional methods for synthesizing these valuable methyl-substituted heterocycles often involve enzymatic processes or complex procedures auxiliaries, limiting the substrate scope efficiency. Efficient catalytic methylation, especially an enantioselective manner, has been a long-standing challenge chemical synthesis. Herein, we present novel approach remote stereoselective installation of methyl group onto N-heterocycles, leveraging CoH-catalyzed asymmetric hydromethylation strategy. By effectively combining commercial cobalt precursor modified bisoxazoline (BOX) ligand, variety easily accessible 3-pyrrolines can be converted to enantiopure 3-(isotopic labeling)methylpyrrolidine compounds outstanding enantioselectivity. This efficient protocol streamlines two-step synthesis enantioenriched which previously required up five six steps under harsh conditions expensive starting materials.

Language: Английский

Citations

3
Photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated olefins with aryl bromides DOI Creative Commons
Hongchao Liu, Xinyu Xu, Siyuan Tang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14865 - 14871

Published: Jan. 1, 2024

A novel photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated alkenes with aryl bromides by using proton as a hydrogen source has been developed for the first time.

Language: Английский

Citations

3
Ni-catalysed remote C(sp3)–H functionalization using chain-walking strategies DOI
Ciro Romano, Rubén Martı́n

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 1, 2024

Language: Английский

Citations

3
Ligand-controlled NiH-catalyzed regiodivergent hydroalkylation of 2-alkenylazaarenes DOI

Ya-Ping Shao,

Zhuomin Chi,

Yong‐Min Liang

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(6), P. 1935 - 1940

Published: April 9, 2024

Language: Английский

Citations

2
Pd(II)-Catalyzed 1,2-Oxyarylation of Alkenes with O-Acylhydroxylamines as the Oxygen Source DOI
Daoming Wang, Lei Yang, Dongping Chen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3691 - 3696

Published: April 25, 2024

O-Acylhydroxylamine has been widely employed as an electrophilic amination reagent in transition-metal-catalyzed C–N coupling reactions, but its use oxygen source not disclosed. Here, we report a Pd-catalyzed 1,2-oxyarylation of alkenes with O-acylhydroxylamines oxidant and for the first time. With simple amide monodentate directing group, this method features broad substrate scope, good functional group tolerance, mild conditions.

Language: Английский

Citations

2
Nickel‐Catalyzed Regio‐ and Enantioselective Migratory Hydrocyanation of Internal Alkenes: Expanding the Scope to α,ω‐Diaryl Internal Alkenes DOI

Mingdong Jiao,

Jinguo Long,

Jianxi Chen

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(21)

Published: March 25, 2024

Abstract Metal‐hydride‐catalyzed migratory functionalization of alkenes witnessed extensive development in the past few years. However, asymmetric version this reaction has remained largely underdeveloped owing to difficulty simultaneous control both regio‐ and stereoselectivity. In addition, exploring wider alkene substrate scope enable more synthetically valuable applications represents another challenge field. context, a nickel‐catalyzed hydrocyanation internal involving chain‐walking process is demonstrated. The exhibits excellent enantioselectivity, proceeds under mild conditions, delivers benzylic nitriles high yields. Even α,ω‐diaryl alkenes, which are known be one most challenging substrates type, could successfully converted desired products with good stereoselectivity by modifying electronic steric effects. Theoretical calculations suggest that η 3 ‐benzyl coordination mode aryl substituent (3,5‐(OMe) 2 C 6 H ) on diphosphite ligand key factors regulating enantioselectivity.

Language: Английский

Citations

0