Strategies and Methods for the Catalytic Asymmetric Synthesis of Benzofuran/Benzopyran Fused Acetals: A Review DOI
Yushuang Chen, Yulong Zhang, Dong Zhang

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(24), P. 4320 - 4333

Published: Nov. 17, 2023

Benzofuran- and benzopyran-fused polycyclic acetals are found in a variety of biologically active natural products. The synthetic methods toward this class heterocycles have fascinated one the most intensive pursuits total synthesis. Nevertheless, stereoselective towards rapid construction such skeletons still remain challenging for organic chemists. Significant progress has been made research area recent years, however, literature on enantioselective approaches to construct these molecules not fully reviewed. Driven by their intriguing complex scaffolds with potential usefulness, we compose advances review covering all important works field. We hope will promote future area.

Language: Английский

Catalytic asymmetric preparation of pyrroloindolines: strategies and applications to total synthesis DOI
Guang‐Jian Mei, Wai Lean Koay,

Chuan Xiang Alvin Tan

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(10), P. 5985 - 6012

Published: Jan. 1, 2021

Pyrroloindolines are widely present in natural products. In this review, we summarize state-of-the-art of catalytic asymmetric synthesis pyrroloindolines, as well related applications to products total synthesis.

Language: Английский

Citations

78
Recent advances in Pd-catalyzed asymmetric cyclization reactions DOI
Bing Xu,

Quanpu Wang,

Chao Fang

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 883 - 971

Published: Dec. 18, 2023

This review aims to collect advancements in enantioselective palladium-catalyzed cyclization reactions over the past eleven years, and it is organized into thirteen sections depending on different types of transformations involved.

Language: Английский

Citations

41
Palladium/TY-Phos-Catalyzed Asymmetric Heck/Tsuji–Trost Reaction of o-Bromophenols with 1,3-Dienes DOI

Youshao Tu,

Bing Xu, Qian Wang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(8), P. 4378 - 4383

Published: Feb. 16, 2023

2,3-Dihydrobenzofurans are crucial building blocks in the synthesis of natural products and pharmaceutical molecules. However, their asymmetric has been a long-standing formidable challenge so far. In this work, we developed highly enantioselective Pd/TY-Phos-catalyzed Heck/Tsuji-Trost reaction o-bromophenols with various 1,3-dienes, allowing expedient access to chiral substituted 2,3-dihydrobenzofurans. This features excellent regio- enantiocontrol, high functional group tolerance, easy scalability. More importantly, demonstration method as valuable tool for construction optically pure (R)-tremetone fomannoxin is highlighted.

Language: Английский

Citations

28
Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis DOI
Wenbo Li, Junliang Zhang

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 31, 2024

ConspectusPalladium catalysis, as one of the most important strategies in asymmetric synthesis, has continuously attracted attention organic chemists. With development chiral ligands, increasingly challenging reactions and substantial progress catalysis are being realized.Since 2014, we have focused on exploiting a series sulfinamide phosphine ligands called "Sadphos," including Ming-Phos, Xu-Phos, Xiao-Phos, Xiang-Phos, TY-Phos, PC-Phos, GF-Phos, WJ-Phos. These can be easily prepared two to four steps using commercial materials. new types shown remarkable performance transition-metal-catalyzed reactions, especially Pd-catalyzed transformations. X-ray diffraction analysis, mechanistic studies, density functional theory calculations revealed that Sadphos coordinate with Pd0 PdII species Pd0/P, Pd0/P,S, or PdII/P,O modes.This Account summarizes our recent efforts toward palladium-catalyzed enantioselective ligands. were found privileged very crucial promote by increasing reactivity enantioselectivity. Ming-Phos is an effective ligand coupling intramolecular Heck providing highly trisubstituted allenes, axially anilides, gem-diarylmethine silanes, disubstituted dihydroisoquinolinones. Incorporation electron-rich cyclohexyl group moiety afforded which showed unique effect transformations, reductive Heck, dearomative Mizoroki–Heck, tandem Heck/Suzuki coupling, carboiodination, carboamination, cross-coupling reactions. Using similar strategy, synthesized more electron–rich TY-Phos Xiang-Phos bearing t-butyl 1-adamantyl at P atoms, respectively. Regarding stereoelectronic features, these characteristic best choice satisfy requirements fluoroarylation gem-difluoroalkenes, intermolecular α-arylation aldehydes, carboetherification alkenyl oximes, carboheterofunctionalization 2,3-dihydrofurans. Compared aforementioned attractive features high nucleophilicity originating from CH2PPh2 ortho-substituent side aryl ring, presumably responsible for its efficiency. The Pd/Xiao-Phos catalyst system shows good secondary oxides, affording P-stereogenic products multiple molecular skeletons. modification basic backbone introducing xanthene skeleton motivated us design synthesize monophosphines, named PC-Phos GF-Phos. various arylation sulfenate anions, denitrogenative cyclization benzotriazoles, dearomatization indoles. practicability GF-Phos was validated three-component N-tosylhydrazones, halides, terminal alkynes, well N-tosylhydrazones vinyl iodides pendent amines. In addition, ferrocene-derived WJ-Phos employed Suzuki–Miyaura reaction, biaryl monophosphine oxides excellent enantiomeric excesses.

Language: Английский

Citations

15
Enantioselective synthesis of isoxazolines bearing allenes by palladium-catalyzed carboetherification of β,γ-unsaturated ketoximes with propargylic acetates DOI

Feifei Jin,

Cangzhu Hu,

Shuaijie Wu

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Enantioselective synthesis of isoxazolines bearing allenes by palladium catalyzed carboetherification alkenyl oximes with propargylic acetates. DFT calculations carried out to disclose the detailed mechanism and origins enantioselectivity.

Language: Английский

Citations

1
Simultaneous construction of axial and planar chirality by gold/TY-Phos-catalyzed asymmetric hydroarylation DOI Creative Commons
Peichao Zhang, Yin-Lin Li, Jiafeng He

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: July 29, 2021

Abstract The simultaneous construction of two different chiralities via a simple operation poses considerable challenge. Herein cationic gold-catalyzed asymmetric hydroarylation ortho-alkynylaryl ferrocenes derivatives is developed, which enable the axial and planar chirality. here identified TY-Phos derived gold complex responsible for high yield, good diastereoselectivity (>20:1 dr), enantioselectivities (up to 99% ee) mild conditions. catalyst system also shows potential application in synthesis chiral biaryl compounds. cause enantioselectivity this investigated with density functional theory caculation.

Language: Английский

Citations

51
Palladium-Catalyzed Asymmetric Tandem Denitrogenative Heck/Tsuji–Trost of Benzotriazoles with 1,3-Dienes DOI
Yin-Lin Li, Peichao Zhang, Haihong Wu

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(33), P. 13010 - 13015

Published: Aug. 17, 2021

The asymmetric denitrogenative cycloaddition has emerged as a powerful tool to build chiral aza-heterocyles. However, only one example of benzotriazole with unsaturated hydrocarbons been explored so far, because the ring-opening generate α-imino metal carbenoid species is thermodynamically unfavorable process. We herein report an efficient benzotriazoles cyclic and acyclic 1,3-dienes enabled by Pd sulfonamide phosphine ligand. A variety substituted hexahydrocarbazoles indolines were delivered in good yields high ee values. Interestingly, pair enantiomers could be obtained use Xu1 PC2 same absolute configuration. synthetic utilities optically active also showcased.

Language: Английский

Citations

51
Regio‐ and Stereoselective Cascade of β,γ‐Unsaturated Ketones by Dipeptided Phosphonium Salt Catalysis: Stereospecific Construction of Dihydrofuro‐Fused [2,3‐b] Skeletons DOI
Hongkui Zhang, Jiajia He, Ya‐Yun Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(36), P. 19860 - 19870

Published: July 2, 2021

Abstract Chiral (dihydro)furo‐fused heterocycles are significant structural motifs in numerous natural products, functional materials and pharmaceuticals. Therefore, developing efficient methods for preparing compounds with these privileged scaffolds is an important endeavor synthetic chemistry. Herein, we develop effective, modular method by a dipeptide‐phosphonium salt‐catalyzed regio‐ stereoselective cascade reaction of readily available linear β,γ‐unsaturated ketones aromatic alkenes, affording wide variety structurally fused heterocyclic molecules high yields excellent stereoselectivities. Moreover, mechanistic investigations revealed that the bifunctional phosphonium salt controlled stereoselectivities this reaction, particularly proceeding through initial ketone α‐addition followed O ‐participated substitution; multiple hydrogen‐bonding interactions between Brønsted acid moieties catalyst nitro group alkene were crucial asymmetric induction. Given generality, versatility, efficiency method, anticipate it will have broad utilities.

Language: Английский

Citations

45
A Counterion/Ligand-Tuned Chemo- and Enantioselective Copper-Catalyzed Intermolecular Radical 1,2-Carboamination of Alkenes DOI

Xian-Yan Cheng,

Yufeng Zhang, Jiahuan Wang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(39), P. 18081 - 18089

Published: Sept. 26, 2022

The copper-catalyzed enantioselective intermolecular radical 1,2-carboamination of alkenes with readily accessible alkyl halides is an appealing strategy for producing chiral amine scaffolds. challenge arises from the easily occurring atom transfer addition between and issue enantiocontrol. We herein describe a alkene sulfoximines in highly chemo- manner. key to success this process conceptual design counterion/highly sterically demanded ligand coeffect promote exchange copper(I) forge C–N bonds radicals copper(II) complex. reaction covers bearing distinct electronic properties, such as aryl-, heteroaryl-, carbonyl-, aminocarbonyl-substituted ones, various precursors, including chlorides, bromides, iodides, CF3 source. Facile transformations deliver many building blocks interest organic synthesis related areas.

Language: Английский

Citations

33
Pd/Ming-Phos-Catalyzed Asymmetric Three-Component Arylsilylation of N-Sulfonylhydrazones: Enantioselective Synthesis of gem-Diarylmethine Silanes DOI
Bin Yang,

Kangning Cao,

Guofeng Zhao

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(34), P. 15468 - 15474

Published: Aug. 22, 2022

A Pd-catalyzed enantioselective three-component reaction of N-sulfonylhydrazones, aryl bromides, and silylboronic esters is developed, enabling the synthesis chiral gem-diarylmethine silanes in high enantioselectivity with use a newly identified Ming-Phos. Compared N-tosyl, more easily decomposed N-mesitylsulfonyl suitable as masking group electron-rich hydrazone to improve efficiency. The features broad scope concerning both coupling partners, enantioselectivity, mild conditions. ready access enantiomers utility this catalytic method are also presented.

Language: Английский

Citations

29