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

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

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Synthetic strategies and mechanistic studies of axially chiral styrenes

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

Published: April 6, 2023

Language: Английский

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Enantioselective copper-catalyzed hydrophosphination of alkenyl isoquinolines

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

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

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

Published: Feb. 1, 2024

Language: Английский

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Synthesis of Alkene Atropisomers with Multiple Stereogenic Elements via Catalytic Asymmetric Rearrangement of 3‐Indolylmethanols

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

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Organocatalytic Atroposelective Hydroselenation of Alkynes To Access Axially Chiral Vinyl Selenides

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

Published: Feb. 20, 2025

Language: Английский

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

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

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

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

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Enantio‐ and Regioselective Cascade Hydroboration of Methylenecyclopropanes for Facile Access to Chiral 1,3‐ and 1,4‐Bis(boronates)

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

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Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes

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

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