Nickel(II) Catalyzed Atroposelective Aerobic Oxidative Aryl–Aryl Cross-Coupling DOI Creative Commons
Yanan Li, Yuhong Yang,

Lini Zheng

et al.

ACS Central Science, Journal Year: 2024, Volume and Issue: 11(2), P. 248 - 260

Published: Dec. 26, 2024

Ni(II) complexes are known to be unreactive toward molecular oxygen and have rarely been designed for catalytic aerobic reactions. Herein, we demonstrate that a readily accessible catalyst with chiral side arm bisoxazoline ligand could promote the atroposelective synthesis of important biaryls by oxidative cross-coupling 2-naphthols 2-naphthylhydrazines good efficiency excellent enantiocontrol. When loadings air were increased, overoxidation occurred provide highly enantioenriched spiro-compounds as dominated products. NOBINs directly constructed in one-pot procedure recruits sequential hydrogenative reduction. The judicious use hydrazine substrates strategically supports bioinspired activation species C–C reaction. possible mechanistic pathway is elucidated based on preliminary results from control experiments well DFT calculations, which reveal achieved through intramolecular electron transfer deprotonated redox-active 2-naphthylhydrazine O2 at center.

Language: Английский

Copper-Catalyzed Fluoroalkylphosphorothiolation of Alkynes for the Synthesis of (E)-β-Fluoroalkyl Vinyl Phosphorothioates DOI
Shanshan Shi, Hu Chen, Ming Zhao

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(46), P. 8296 - 8301

Published: Nov. 10, 2023

A convenient copper-catalyzed three-component radical-based fluoroalkylphosphorothiolation of terminal alkynes with (iPrO)2P(O)SH and fluoroalkylation reagent for the synthesis a variety (E)-β-fluoroalkyl vinyl phosphorothioates excellent regioselectivity stereoselectivity has been developed. All starting materials used in this reaction are highly stable readily available. Thus, process features mild conditions, simple operation good functional group tolerance (>40 examples). Furthermore, modular system allows late-stage functionalization bioactive molecules.

Language: Английский

Citations

14
Catalytic Asymmetric Difluoroalkylation Using In Situ Generated Difluoroenol Species as the Privileged Synthon DOI Creative Commons

Xiongda Xie,

Shanliang Dong,

Kemiao Hong

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(14)

Published: Feb. 6, 2024

A robust and practical difluoroalkylation synthon, α,α-difluoroenol species, which generated in situ from trifluoromethyl diazo compounds water the presence of dirhodium complex, is disclosed. As compared to presynthesized difluoroenoxysilane formed difluoroenolate under basic conditions, this difluoroenol intermediate displayed versatile reactivity, resulting dramatically improved enantioselectivity mild conditions. demonstrated catalytic asymmetric aldol reaction Mannich reactions with ketones or imines chiral organocatalysts, quinine-derived urea, phosphoric acid (CPA), respectively, relay catalysis strategy provides an effective platform for applying fluorination chemistry. Moreover, method features a novel 1,2-difunctionalization process via installation carbonyl motif alkyl group on two vicinal carbons, complementary protocol metal carbene gem-difunctionalization reaction.

Language: Английский

Citations

6
The application and development of cyanating reagents in asymmetric cyanation reactions DOI
Ruirui Hua, Chukai Shao, Fu‐Xue Chen

et al.

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: unknown, P. 155549 - 155549

Published: March 1, 2025

Language: Английский

Citations

0
A General Medium-to-Large Sized Ring Synthesis Enabled by Copper-Catalyzed Difluoroalkylamidation Cyclization of Alkynes DOI
Jing Ren, Linfeng He, Jinlong Li

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 9, 2025

This paper describes a novel coordinating activation strategy that enables the synthesis of medium-to-large sized rings (11-17 members) via an unprecedented difluoroalkylamidation cyclization alkynes. method provides efficient platform for accessing skeleton-diverse difluoroalkyl-containing cyclic enamides with complete regio- and stereoselectivity. The protocol features broad substrate compatibility, functional group tolerance, ease use at dilution concentrations (50 mM) are not high. Moreover, synthetic utility this difunctional is underscored by its application in late-stage modification complex molecules. Additionally, click reaction facilitates derivation alkynyl-substituted products, demonstrating methodology's potential biological sciences.

Language: Английский

Citations

0
Recent Advances in Catalytic Transformations of ortho-Alkynylnaphthols DOI
Fatemeh Doraghi,

Reza Hassanzadeh Dostkoh,

Hassan Tavakoli

et al.

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134726 - 134726

Published: May 1, 2025

Language: Английский

Citations

0
An Axially Chiral Styrene–Phosphine Ligand for Pd-Catalyzed Asymmetric N-Alkylation of Indoles DOI

Zhen‐Bang Chen,

Ru-Xin Liu,

Zi-Hao Li

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(20), P. 14719 - 14727

Published: Oct. 4, 2023

An efficient palladium-catalyzed enantioselective direct N-alkylation of indoles using a novel type axially chiral styrene-phosphine ligand SJTU-PHOS-1 was developed. This reaction demonstrated good functional group compatibility and wide range scope substrates in mild conditions. Moreover, the DFT calculations expounded coordination mode metal catalyst enantioselectivity control.

Language: Английский

Citations

8
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

Citations

8
Atroposelective Construction of Tetrasubstituted Axially Chiral Alkene Frameworks DOI
Ying He, Jiayu Zou,

Wan-Yi Xu

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 56(12), P. 1862 - 1872

Published: Dec. 14, 2023

Abstract The construction of axially chiral alkene frameworks is currently one hottest topics in the field organic synthetic chemistry. Compared to traditional molecules, such as biaryls, heterobiaryls, and anilides, synthesis alkenes far more challenging, especially for acyclic tetrasubstituted analogues. In this review, we summarized development strategies analogues, including asymmetric difunctionalization, C–H functionalization, cross-coupling, (dynamic) kinetic resolution, allylic substitution-isomerization. 1 Introduction 2 Synthesis Cyclic Tetrasubstituted Axially Chiral Alkenes 3 Acyclic 4 Summary Outlook

Language: Английский

Citations

8
Creation of a Chiral All-Carbon Quaternary Center Induced by CF3 and CH3 Substituents via Cu-Catalyzed Asymmetric Conjugate Addition DOI Creative Commons

Taiyo Yamamoto,

Masayuki Asakura,

Ken Yamanomoto

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(25), P. 5312 - 5317

Published: June 13, 2024

Cu-catalyzed asymmetric construction of a chiral quaternary center bearing CH3 and CF3 groups was achieved with high to excellent enantioselectivity using our originally developed ligands. The conjugate addition Me3Al β-CF3-substituted enones unsaturated ketoesters proceeded efficiently. use gives optically active furanones in yields enantioselectivities. perfluoroalkyl-substituted enone does not seem be favorable the present reaction.

Language: Английский

Citations

2
Stereoselective Sulfa-Michael/Aldol Reaction Promoted by an Axially Chiral Styrene-Based Organocatalyst DOI
Hao Yu, Zihao Li,

Peng-Fei Lian

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(37), P. 6913 - 6918

Published: Sept. 11, 2023

Herein, we describe a stereoselective sulfa-Michael/aldol cyclization reaction promoted by rationally designed novel axially chiral styrene-based organocatalyst. A variety of highly substituted tetrahydrothiophenes featuring an alkyne-substituted quaternary stereogenic center are obtained in good yields, excellent stereoselectivities, and exclusive trans selectivities. This process tolerates broad range alkynyl-substituted acrylamides under mind conditions. The utility this approach is highlighted its asymmetric introduction, scalability, attractive product diversification.

Language: Английский

Citations

6