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

Stereodivergent Construction of 1,3‐Chiral Centers via Tandem Asymmetric Conjugate Addition and Allylic Substitution Reaction DOI
Jia‐Hao Xie,

Yi‐Ming Hou,

Zuolijun Feng

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(10)

Published: Jan. 4, 2023

Herein, we report a synthesis of cyclohexanones bearing multi-continuous stereocenters by combining copper-catalyzed asymmetric conjugate addition dialkylzinc reagents to cyclic enones with iridium-catalyzed allylic substitution reaction. Good excellent yields, diastereoselectivity and enantioselectivity can be obtained. Unlike the stereodivergent construction adjacent (1,2-position) reported in literature, current reaction achieve nonadjacent (1,3-position) proper combination two chiral catalysts different enantiomers.

Language: Английский

Citations

34
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

34
Recent advances in the construction of axially chiral arylpyrroles DOI

Yang‐Bo Chen,

Ye-Nan Yang,

Xuan-Zhu Huo

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(9), P. 2480 - 2491

Published: Aug. 9, 2023

Language: Английский

Citations

30
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
Ir‐Catalyzed Enantioselective Synthesis of gem‐Diborylalkenes Enabled by 1,2‐Boron Shift DOI

Jianfei Ge,

Xi‐Zhang Zou,

Xinru Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(32)

Published: June 15, 2023

Abstract Asymmetric cross‐couplings based on 1,2‐carbon migration from B‐ate complexes have been developed efficiently to access valuable organoboronates. However, enantioselective reactions triggered by 1,2‐boron shift remained be unaddressed synthetic challenge. Here, Ir‐catalyzed asymmetric allylic alkylation enabled was developed. In this reaction, we disclosed that excellent enantioselectivities were achieved through an interesting dynamic kinetic resolution (DKR) process of carbonates at the elevated temperature. Notably, highly (bis‐boryl)alkenes array diversifications versatile molecules. Extensive experimental and computational studies conducted elucidate reaction mechanism DKR clarify origin enantioselectivities.

Language: Английский

Citations

27
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

9
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
Palladium-Catalyzed Modular and Enantioselective cis-Difunctionalization of 1,3-Enynes with Imines and Boronic Reagents DOI
Qing He, Lei Zhu,

Zhen‐Hong Yang

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(43), P. 17989 - 17994

Published: Oct. 20, 2021

Here we report that a palladium(0) complex can mediate the unprecedented intermolecular coupling reaction of 1,3-enynes and N-sulfonylimines regio- stereoselectively, resultant palladium(II) species undergo cascade Suzuki with organoboronic reagents. The substrate scope is substantial for asymmetric three-component process, enantioenriched all-carbon tetra-substituted alkene derivatives are efficiently constructed in modular cis-difunctionalized manner. Control experiments density functional theory (DFT) calculations support idea acts as π-Lewis base catalyst by chemoselectively forming η2-complexes moiety 1,3-enynes, thus increasing nucleophilicity alkyne group based on principle vinylogy, to attack imines enantioselectively. preferable formation aza-palladacyclopentene intermediates, via 90° single bond rotation from π-allyl complex, guarantees formal cis-carbopalladation group. In addition, palladium(0)-catalyzed enantioselective reductive 1,3-enyne imine realized using formic acid hydrogen transfer reagent.

Language: Английский

Citations

52
Development of Axially Chiral Styrene-Type Carboxylic Acid Ligands via Palladium-Catalyzed Asymmetric C–H Alkynylation DOI

Chi Yang,

Fei Li,

Tian-Rui Wu

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(21), P. 8132 - 8137

Published: Oct. 14, 2021

A weakly coordinated carboxylate-directed palladium-catalyzed atroposelective C-H alkynylation method for the development of novel axially chiral styrene-type carboxylic acids is disclosed. This transformation exhibits good yields (up to 85%), excellent enantiocontrol 99% ee), and mild conditions. Notably, synthetic utility resulting alkynyl acid derivatives was demonstrated by various derivatizations as well their potential ligands in asymmetric activations.

Language: Английский

Citations

41
Asymmetric Construction of an Aryl‐Alkene Axis by Palladium‐Catalyzed Suzuki–Miyaura Coupling Reaction DOI

Sheng‐Qi Qiu,

Yu Chen,

Xiang‐Jun Peng

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(45)

Published: Sept. 16, 2022

The application of Suzuki-Miyaura coupling reaction to forge the atropisomeric biaryls has seen remarkable progress but exploration this chemistry directly chiral C(aryl)-C(alkene) axis is underdeveloped. replacement arene substrates by alkenes intensifies challenges in terms reactivity, configurational atropostability product and selectivity control. By meticulous ligand design fine-tuning parameters, we identified a highly active 3,3'-triphenylsilyl-substituted phosphite realize arene-alkene hindered aryl halides vinyl boronates under very mild conditions. axially acyclic aryl-alkenes were generated commendable efficiency, enantioselectivity E/Z selectivity.

Language: Английский

Citations

37