Rhodium(I)‐Catalyzed Asymmetric Hydroarylative Cyclization of 1,6‐Diynes to Access Atropisomerically Labile Chiral Dienes DOI
Panjie Hu,

Lingfei Hu,

Xiao‐Xi Li

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 16, 2023

Abstract Axially chiral open‐chained olefins are an underexplored class of atropisomers, whose enantioselective synthesis represents a daunting challenge due to their relatively low racemization barrier. We herein report rhodium(I)‐catalyzed hydroarylative cyclization 1,6‐diynes with three distinct classes arenes, enabling highly broad range axially 1,3‐dienes that conformationally labile (Δ G ≠ ( rac )=26.6–28.0 kcal/mol). The coupling reactions in each category proceeded excellent enantioselectivity, regioselectivity, and Z/E selectivity under mild reaction conditions. Computational studies the quinoline N ‐oxide system reveal proceeds via initial oxidative 1,6‐diyne give rhodacyclic intermediate, followed by σ‐bond metathesis between arene C−H bond Rh−C(vinyl) bond, subsequent C−C reductive elimination being enantio‐determining turnover‐limiting. DFT‐established mechanism is consistent experimental studies. coupled products ‐oxides undergo facile visible light‐induced intramolecular oxygen‐atom transfer, affording epoxides complete axial‐to‐central chirality transfer.

Language: Английский

Controlling Stereoselectivity with Noncovalent Interactions in Chiral Phosphoric Acid Organocatalysis DOI
Isaiah O. Betinol, Yutao Kuang,

Brian P. Mulley

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Chiral phosphoric acids (CPAs) have emerged as highly effective Brønsted acid catalysts in an expanding range of asymmetric transformations, often through novel multifunctional substrate activation modes. Versatile and broadly appealing, these benefit from modular tunable structures, compatibility with additives. Given the unique types noncovalent interactions (NCIs) that can be established between CPAs various reactants─such hydrogen bonding, aromatic interactions, van der Waals forces─it is unsurprising catalyst systems become a promising approach for accessing diverse chiral product outcomes. This review aims to provide in-depth exploration mechanisms by which impart stereoselectivity, positioning NCIs central feature connects broad spectrum catalytic reactions. Spanning literature 2004 2024, it covers nucleophilic additions, radical atroposelective bond formations, highlighting applicability CPA organocatalysis. Special emphasis placed on structural mechanistic features govern CPA-substrate well tools techniques developed enhance our understanding their behavior. In addition emphasizing details stereocontrolling elements individual reactions, we carefully structured this natural progression specifics broader, class-level perspective. Overall, findings underscore critical role catalysis significant contributions advancing synthesis.

Language: Английский

Citations

3
Control of Axial Chirality through NiH-Catalyzed Atroposelective Hydrofunctionalization of Alkynes DOI

Feng‐Tao Sheng,

Shi‐Chao Wang,

Junqian Zhou

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(6), P. 3841 - 3846

Published: March 3, 2023

Catalytic asymmetric hydrofunctionalization of alkenes is a well-established method with which to construct complex C(sp3)-enriched molecules central chirality. In contrast, the use catalytic abundant alkyne substrates produce valuable multisubstituted axial chirality remains largely unexplored. Here, we report general procedure this type catalyzed by Ni(II) salts and employing structurally simple chiral PyrOx ligand. A wide variety diverse atropisomeric styrenes have been obtained from hydroarylation alkynes high efficiency, complete Z-selectivity, excellent enantioselectivity.

Language: Английский

Citations

36
Enantioselective copper-catalyzed hydrophosphination of alkenyl isoquinolines DOI Creative Commons
Qingjing Yang, Jian Zhou, Jun Wang

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(16), P. 4413 - 4417

Published: Jan. 1, 2023

An enantioselective hydrophosphination of alkenyl isoquinolines is developed by using a copper-chiral diphosphine ligand catalyst. It provides direct and atom-efficient approach to prepare variety chiral phosphines with an isoquinoline unit in good yields high enantioselectivities. In addition, these phosphine products are useful bidentate P,N-ligands which showed potential application asymmetric catalysis.

Language: Английский

Citations

27
Synthetic strategies and mechanistic studies of axially chiral styrenes DOI Creative Commons

Zi-Hao Li,

Quan‐Zhe Li,

He‐Yuan Bai

et al.

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(6), P. 100594 - 100594

Published: April 6, 2023

Language: Английский

Citations

27
Ni-catalyzed propargylic substitution reaction: A general and versatile tool to assemble axially chiral phosphorus-containing allenes DOI Open Access

Xiao-dong Gu,

Ka Yan Ngai, Wei Wang

et al.

Chem Catalysis, Journal Year: 2024, Volume and Issue: 4(3), P. 100903 - 100903

Published: Feb. 1, 2024

Language: Английский

Citations

12
Enantio‐ and Regioselective Cascade Hydroboration of Methylenecyclopropanes for Facile Access to Chiral 1,3‐ and 1,4‐Bis(boronates) DOI Creative Commons
Jian Zhou, Ling Meng,

Ziyi Yang

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(21)

Published: March 13, 2024

Abstract Chiral 1, n‐bis(boronate) plays a crucial role in organic synthesis and medicinal chemistry. However, their catalytic asymmetric has long posed challenge terms of operability accessibility from readily available substrates. The recent discovery the C═C bond formation through β‐C elimination methylenecyclopropanes (MCP) provided an exciting opportunity to enhance molecular complexity. In this study, catalyzed cascade hydroboration MCP is developed. By employing different ligands, various homoallylic boronate intermediate are obtained ring opening process. Subsequently, with HBpin or B 2 pin resulted enantioenriched chiral 1,3‐ 1,4‐bis(boronates) high yields, accompanied by excellent chemo‐ enantioselectivities. selective transformation these two distinct C─B bonds also demonstrated application potential synthesis.

Language: Английский

Citations

10
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
Synthesis of Alkene Atropisomers with Multiple Stereogenic Elements via Catalytic Asymmetric Rearrangement of 3‐Indolylmethanols DOI
Ping Wu,

Wen‐Tao Zhang,

Jixiang Yang

et al.

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

Published: July 23, 2024

Abstract Catalytic enantioselective preparation of alkene atropisomers with multiple stereogenic elements and discovery their applications have become significant but challenging issues in the scientific community due to unique structures this class atropisomers. We herein report first catalytic atroposelective cyclopentenyl[ b ]indoles, a new kind atropisomers, point axial chirality via an unusual rearrangement reaction 3‐indolylmethanols under asymmetric organocatalysis. Notably, novel type promising developing chiral ligands or organocatalysts, discovering antitumor drug candidates fluorescence imaging materials. Moreover, theoretical calculations elucidated possible mechanism non‐covalent interactions control enantioselectivity. This approach offers synthetic strategy for elements, represents 3‐indolylmethanols, which will advance chemistry indole chemistry.

Language: Английский

Citations

10
Enantioselective Zn-Catalyzed Hydrophosphinylation of Nitrones: An Efficient Approach for Constructing Chiral α-Hydroxyamino-Phosphine Oxides DOI Creative Commons

Shihui Luo,

Xiaohong Yuan,

Jiangtao Cheng

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Although enantioselective hydrofunctionalizations of nitrones are established for synthesis various types chiral hydroxylamines, the asymmetric catalytic hydrophosphinylation remains highly challenging. Herein, an efficient of...

Language: Английский

Citations

1
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