Atroposelective Three-Component (Fluoro)methylative Alkylation of Terminal Alkynes DOI

Yaheng Zhao,

Liping Huo,

Xiaoyu Zhao

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 63 - 71

Published: Dec. 13, 2024

The development of synthetic methods for the selective installation methyl and fluoromethyl groups is highly desired due to their critical role in drug development. While significant advances have been made methylation difluoromethylation aromatic compounds, catalytic atroposelective (fluoro)methylative functionalization alkynes forge axially chiral alkenes remains underexploited. Herein, we report an enantioselective cross-electrophile strategy efficient 1,2-carbo-(fluoro)methylation with two different alkyl halides via nickel catalysis. By integrating a one-electron radical process two-electron organometallic process, this protocol employs simple catalyst effectively discriminate between secondary tertiary (fluoro)methyl alkyne difunctionalization. This demonstrates good compatibility activated secondary/tertiary bromides, terminal alkynes, halides, permitting straightforward synthesis broad range synthetically valuable (fluoro)methyl-substituted high chemo-, regio-, trans-, atropo-selectivity. Preliminary mechanistic studies provide insight into potential reaction pathway.

Language: Английский

Atroposelective catalysis DOI

Tanno A. Schmidt,

Valeriia Hutskalova,

Christof Sparr

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(7), P. 497 - 517

Published: June 18, 2024

Language: Английский

Citations

21
Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes DOI
Pu‐Fan Qian, Tao Zhou, Bing‐Feng Shi

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(85), P. 12669 - 12684

Published: Jan. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Language: Английский

Citations

43
Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes DOI
Wangyang Li, Haohua Chen,

Yanping Zheng

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11318 - 11331

Published: July 15, 2024

Catalytic enantioselective borylation reactions of unsaturated bonds as powerful tools for the synthesis diverse chiral organoboron compounds have gained much attention and wide applications in various fields. However, atroposelective arylboration reaction with carbon–carbon triple 1,3-enynes to obtain axially 1,3-dienylboronates remains an elusive significant challenge. Hence, we develop a cooperative copper- palladium-catalyzed assemble plentiful function enriched single step from easily available 1,3-enynes, B2pin2, aryl bromides high levels chemo-, regio-, stereo-, atroposelectivity. The mild conditions lead good functional group tolerance, which is proven by broad substrate scope late-stage functionalizations bioactive or drug molecules. Moreover, can be scaled up, series further transformations achieved. It worth emphasizing that several olefin catalysts ligands axial chirality also synthesized through corresponding elaborations such products, explains transformative ability application potential 1,3-dienylboronates. mechanism experiment density theory (DFT) calculations revealed process copper palladium catalysis, indicating chemoselectivity regioselectivity boration are determined enyne insertion on copper, atroposelectivity controlled reductive elimination center. Meanwhile, calculation demonstrated distinct interactions between P═O C═O groups Pd Bpin center key transition state formation products varying configurations while employing identical configuration ligands.

Language: Английский

Citations

10
NiH-Catalyzed Regio- and Enantioselective Hydroalkylation for the Synthesis of β- or γ-Branched Chiral Aromatic N-Heterocycles DOI
Ju‐Song Yang,

Ka Lu,

Chen‐Xiao Li

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(40), P. 22122 - 22134

Published: Sept. 25, 2023

A nickel hydride-catalyzed regio- and enantioselective hydroalkylation reaction was developed to give access a library of chiral β- or γ-branched aromatic N-heterocycles. This intriguing asymmetric transformation features excellent selectivities, step- atom-economies, generating two kinds products through one synthetic strategy. Furthermore, the possible mechanism extensively investigated using numerous control experiments density functional theory calculations.

Language: Английский

Citations

22
Atroposelective Synthesis of Axially Chiral Styrenes by Platinum‐ Catalyzed Stereoselective Hydrosilylation of Internal Alkynes DOI

Qimin Wu,

Qi Zhang, Shuxin Yin

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: May 25, 2023

Abstract Hydrofunctionalization of alkynes is one the most efficient ways to access axially chiral styrenes with open‐chained olefins. While great advances have been achieved for 1‐alkynylnaphthalen‐2‐ols and analogues, atroposelective hydrofunctionalization unactivated internal lags. Herein we reported a platinum‐catalyzed hydrosilylation first time. With monodentate TADDOL‐derived phosphonite L1 used as ligand, various were in excellent enantioselectivities high E ‐selectivities. Control experiments showed that N H‐arylamide groups significant effects on both yields could act directing groups. The potential utilities products shown by transformations amide motifs products.

Language: Английский

Citations

20
Ligand-Controlled Regiodivergent Ring Expansion of Benzosilacyclobutenes with Alkynes en Route to Axially Chiral Silacyclohexenyl Arenes DOI

Xiaoxiao Tang,

Yulang Tang,

Ju Peng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 21, 2024

A ligand-controlled regiodivergent and enantioselective ring expansion of benzosilacyclobutenes with internal naphthyl alkynes has been achieved by adjusting the ligand cavity size. The (

Language: Английский

Citations

7
Organocatalytic Atroposelective Hydroselenation of Alkynes To Access Axially Chiral Vinyl Selenides DOI

Yi-Xin Wang,

Jing-Run Wang,

Chen Cui

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4051 - 4060

Published: Feb. 20, 2025

Language: Английский

Citations

1
Rhodium-catalyzed atroposelective access to trisubstituted olefinsviaC–H bond olefination of diverse arenes DOI Creative Commons
Xiaohan Zhu,

Ruijie Mi,

Jie Yin

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(29), P. 7999 - 8005

Published: Jan. 1, 2023

The atroposelective synthesis of axially chiral acyclic olefins remains a daunting challenge due to their relatively lower racemization barriers, especially for trisubstituted ones. In this work, C-H olefination has been realized open-chain via activation two classes (hetero)arenes in the coupling with sterically hindered alkynes. employment phenyl N-methoxycarbamates as arene reagents afforded phenol-tethered olefins, carbamate being traceless directing group. N-methoxy-2-indolylcarboxamides corresponding olefin by circumventing redox-neutral [4 + 2] annulation. reactions proceeded excellent Z/E selectivity, chemoselectivity, regioselectivity, and enantioselectivity both hydroarylation systems.

Language: Английский

Citations

14
Silanes as a versatile hydride source for Ni–H catalysis: a promising tool for π-hydro functionalization DOI
Yafia Kousin Mirza, Partha Sarathi Bera, Sachin Balaso Mohite

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(15), P. 4290 - 4317

Published: Jan. 1, 2024

Nickel-catalyzed hydrofunctionalization of π-substrates is a possibly effective method to synthesize several value-added molecular architectures. This review covers the NiH catalyzed reactions alkenes, alkynes and allenes.

Language: Английский

Citations

6
Rhodium-Catalyzed Asymmetric Hydroselenation of 1-Alkynylindoles for Atroposelective Synthesis of Vinyl Selenoethers DOI

Yulong Kang,

Fen Wang, Xingwei Li

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(17), P. 13055 - 13064

Published: Aug. 15, 2024

Catalytic asymmetric hydrofunctionalization of π-bonds has been extensively studied, but the alkynes that affords atropoisometric products remains heavily underexplored. We herein report [Rh(COD)OAc]2/Mg(NTf2)2-catayzed highly atroposelective hydroselenation two classes 1-alkynylindoles using selenophenols, where Mg(II) salt both activates Rh catalyst and provides a key NTf2 anion essential for catalytic activity enantioselectivity, affording C–N axially chiral trisubstituted olefins bear relatively low racemization barrier (ΔG‡ ∼ 27 kcal/mol). The system features high activity, mild reaction conditions, good functional group tolerance, regio-, (E)-, enantioselectivity. selenoether moiety in product framework can be readily functionalized to give synthetically useful products.

Language: Английский

Citations

5