Axially Chiral Ligands and Catalysts Derived from Atropisomeric Binaphthyl Structures DOI
Shouyi Cen, Zhipeng Zhang

Published: Oct. 18, 2024

The synthesis of 1,1′-bi-2-naphthol (BINOL) can be traced back to about 100 years ago, whereas the utilization BINOL as a chiral ligand was reported by Noyori et al. in 1979. One year later 1980, development and application 2,2′-bis(di-phenylphosphino)-1,1′-binaphthyl (BINAP) reported. This milestone brings axially binaphthyl structures stage asymmetric catalysis inspires large variety ligands organocatalysts possessing axial chirality. chapter traces source chirality, focuses on structural diversity catalysts timeline for their development, introduces 150 representative derived from structures, especially BINOL, 2,2′-diamino-1,1′-binaphthalene (BINAM), 2-amino-2′-hydroxy-1,1′-binaphthyl (NOBIN). With rapid syntheses diversified molecules, it is expected that more novel powerful will developed, tremendous transformations realized future.

Language: Английский

Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents DOI Creative Commons
Akira Yoshimura, Viktor V. Zhdankin

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Language: Английский

Citations

28
Recent advances in catalytic asymmetric synthesis DOI Creative Commons

Ashna Garg,

Dominick Rendina,

Hersh Bendale

et al.

Frontiers in Chemistry, Journal Year: 2024, Volume and Issue: 12

Published: May 9, 2024

Asymmetric catalysis stands at the forefront of modern chemistry, serving as a cornerstone for efficient creation enantiopure chiral molecules characterized by their high selectivity. In this review, we delve into realm asymmetric catalytic reactions, which spans various methodologies, each contributing to broader landscape enantioselective synthesis molecules. Transition metals play central role catalysts wide range transformations with ligands such phosphines, N -heterocyclic carbenes (NHCs), etc., facilitating formation C-C and C-X bonds, enabling precise control over stereochemistry. Enantioselective photocatalytic reactions leverage power light driving force electrocatalysis has emerged sustainable approach, being both atom-efficient environmentally friendly, while offering versatile toolkit reductions oxidations. Biocatalysis relies on nature’s most catalysts, i.e., enzymes, provide exquisite selectivity, well tolerance diverse functional groups under mild conditions. Thus, enzymatic optical resolution, kinetic resolution dynamic have revolutionized production compounds. organocatalysis uses metal-free organocatalysts, consisting modular phosphorus, sulfur nitrogen components, remarkably transformations. Additionally, unlocking traditionally unreactive C-H bonds through selective functionalization expanded arsenal synthesis, atom-economical construction Incorporating flow chemistry been transformative, continuous systems reaction conditions, enhancing efficiency optimization. Researchers are increasingly adopting hybrid approaches that combine multiple strategies synergistically tackle complex synthetic challenges. This convergence holds great promise, propelling field forward in form. As these methodologies evolve complement one another, they push boundaries what can be accomplished leading discovery novel, highly may lead groundbreaking applications across industries.

Language: Английский

Citations

7
Intermolecular α-Functionalization of Benzylamides with N-Nucleophiles via Oxidative Umpolung: Synthesis of Tetrasubstituted 3,3′-Oxindoles DOI
Yue Wang, Jin‐Tao Yu, Yang Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(28), P. 6041 - 6046

Published: July 8, 2024

A hypervalent iodine-mediated intermolecular α-umpolung reaction between α-aryl- or alkyl-substituted amides and benzotriazoles purine derivatives as N-centered nucleophiles has been established. The involves sequential intra/intermolecular oxidative C–N couplings in a controlled manner, affording tetrasubstituted 3,3′-oxindoles moderate to good yields. This approach efficiently addresses the challenges constructing carbon centers via functionalizations of carbonyl compounds serves new strategy for synthesizing biologically important 3,3′-disubstituted oxindoles.

Language: Английский

Citations

4
Helical polyisocyanide-based macroporous organic catalysts for asymmetric Michael addition with high efficiency and stereoselectivity DOI Creative Commons

Xun-Hui Xu,

Run‐Tan Gao,

Shiyi Li

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(31), P. 12480 - 12487

Published: Jan. 1, 2024

Porous materials have attracted interest due to their high specific surface area and rich functionality. Immobilizing organocatalysts onto porous polymers not only boosts enantioselectivity but also improves the reaction rates. In this work, a series of C-poly-3

Language: Английский

Citations

3
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
Chiral Bis(binaphthyl) Cyclopentadienyl Ligands for Rhodium-Catalyzed Desymmetrization of Diarylmethanes via Selective Arene Coordination DOI

Wen‐Qiang Wu,

Pei‐Pei Xie, Leyao Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 18, 2024

Owing to substantial advances in the past several decades, transition-metal-catalyzed asymmetric reactions have garnered considerable attention as pivotal methods for constructing chiral molecules from abundant, readily available achiral counterparts. These are largely attributed development of ligands that control stereochemistry through steric repulsion and other noncovalent interactions between functional groups or prochiral centers on substrates. However, stereocontrol weakens dramatically with increasing distance reaction site group center. Herein, we report a symphonic strategy remote Rh(III)-catalyzed benzylic C-H bond addition diarylmethanes which two aryl motifs differ at

Language: Английский

Citations

1
Regioselective fluorination of allenes enabled by I(I)/I(III) catalysis DOI Creative Commons
Zixuan Wang,

Yameng Xu,

Ryan Gilmour

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: July 9, 2024

Abstract The prominence and versatility of propargylic fluorides in medicinal chemistry, coupled with the potency F/H F/OH bioisosterism, has created a powerful impetus to develop efficient methods facilitate their construction. Motivated by well-established conversion alcohols allenes, an operationally simple, organocatalysis-based strategy process these abundant unsaturated precursors would be highly enabling: this consolidate bioisosteric relationship that connects fluorides. Herein, we describe regioselective fluorination unactivated allenes based on I(I)/I(III) catalysis presence inexpensive HF source serves dual role as both nucleophile Brønsted acid activator. This enables variety secondary tertiary prepared: motifs are prevalent across bioactive small molecule spectrum. Facile product derivatisation, concise synthesis multi-vicinal fluorinated products together preliminary validation enantioselective disclosed. expansive potential platform is also demonstrated through organocatalytic oxidation, chlorination arylation allenes. It envisaged transformation will find application molecular design accelerate exploration organofluorine chemical space.

Language: Английский

Citations

1
Research Progress in the Synthesis of Alkenyl Hypervalent Iodine DOI

冰杰 刘

Journal of Organic Chemistry Research, Journal Year: 2024, Volume and Issue: 12(04), P. 549 - 559

Published: Jan. 1, 2024

Language: Английский

Citations

0
Axially Chiral Ligands and Catalysts Derived from Atropisomeric Binaphthyl Structures DOI
Shouyi Cen, Zhipeng Zhang

Published: Oct. 18, 2024

The synthesis of 1,1′-bi-2-naphthol (BINOL) can be traced back to about 100 years ago, whereas the utilization BINOL as a chiral ligand was reported by Noyori et al. in 1979. One year later 1980, development and application 2,2′-bis(di-phenylphosphino)-1,1′-binaphthyl (BINAP) reported. This milestone brings axially binaphthyl structures stage asymmetric catalysis inspires large variety ligands organocatalysts possessing axial chirality. chapter traces source chirality, focuses on structural diversity catalysts timeline for their development, introduces 150 representative derived from structures, especially BINOL, 2,2′-diamino-1,1′-binaphthalene (BINAM), 2-amino-2′-hydroxy-1,1′-binaphthyl (NOBIN). With rapid syntheses diversified molecules, it is expected that more novel powerful will developed, tremendous transformations realized future.

Language: Английский

Citations

0