Diastereodivergent Catalysis DOI Creative Commons
Daniel Moser,

Tanno A. Schmidt,

Christof Sparr

и другие.

JACS Au, Год журнала: 2023, Номер 3(10), С. 2612 - 2630

Опубликована: Сен. 26, 2023

Alongside enantioselective catalysis, synthetic chemists are often confronted by the challenge of achieving catalyst control over relative configuration to stereodivergently access desired diastereomers. Typically, these approaches iteratively or simultaneously multiple stereogenic units for which dual catalytic methods comprising sequential, relay, and synergistic catalysis emerged as particularly efficient strategies. In this Perspective, benefits challenges catalyst-controlled diastereodivergence in construction carbon stereocenters discussed on basis illustrative examples. The concepts then transferred diastereodivergent atropisomeric systems with twofold higher-order stereogenicity well E- Z-configured alkenes.

Язык: Английский

Bimetallic Catalysis in Stereodivergent Synthesis DOI
Xiaohong Huo, Guanlin Li, Xi Wang

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(45)

Опубликована: Авг. 2, 2022

Abstract Bimetallic catalysis has emerged as an efficient strategy for the development of new chemical reactions. Importantly, this also provides a simple and powerful platform stereodivergent synthesis, whereby all possible stereoisomers products bearing two stereocenters can be easily prepared from same set starting materials. In Minireview, allylic substitution, propargylic hydrofunctionalization, annulation based on bimetallic been summarized. It is expected that more catalytic systems will developed applied synthesis valuable molecules.

Язык: Английский

Процитировано

139
Stereodivergent total synthesis of rocaglaol initiated by synergistic dual-metal-catalyzed asymmetric allylation of benzofuran-3(2H)-one DOI Creative Commons
Yang Xu,

Hongkai Wang,

Zhuang Yang

и другие.

Chem, Год журнала: 2022, Номер 8(7), С. 2011 - 2022

Опубликована: Май 2, 2022

Язык: Английский

Процитировано

87
Synergistic Dual Catalysis in Stereodivergent Synthesis DOI
Liang Wei, Cong Fu,

Zuo-Fei Wang

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(6), С. 3812 - 3844

Опубликована: Фев. 23, 2024

Chiral skeletons with multiple stereogenic centers widely reside in nature and drugs, their relative absolute configuration often determine physiological or pharmacological properties. Stereodivergent synthesis of chiral molecules is not only great significance, but also highly challenging since the formation one diastereomers inherently preferred most asymmetric reactions. dual catalysis, introduced 2013 by Carreira group, perfectly catered to all requirements for full stereoselectivity control given reactions two catalysts are utilized a synergistic way act independently, has now been arguably efficient strategy realize stereodivergent synthesis. This comprehensive review presents an overview development enabled catalysis past ten years, providing readers fundamental attributes as well ability, scope, mechanism, limitations this strategy.

Язык: Английский

Процитировано

31
Pd-Catalyzed Asymmetric Larock Indole Synthesis to Access Axially Chiral N-Arylindoles DOI
Genwei Zhang, Bin Yang, Junfeng Yang

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5493 - 5501

Опубликована: Фев. 13, 2024

Larock indole synthesis is one of the most straightforward and efficient methods for indoles; however, there has been no asymmetric version yet construction indole-based axially chiral N-arylindoles since its initial report in 1991. Herein we first example an by employing a sulfinamide phosphine (SadPhos) ligand (Ming-Phos) with palladium. It allows rapid wide range N-arylindole compounds good yields up to 98:2 er. The application this unique scaffold as organocatalyst promising. Furthermore, kinetic study revealed that alkyne migratory insertion rate-determining step, which proven density functional theory (DFT) calculations. Additionally, DFT studies also suggest N–C dihedral difference caused steric hindrance contributes enantioselectivity control.

Язык: Английский

Процитировано

20
Synergistic Pd/Cu-Catalyzed 1,5-Double Chiral Inductions DOI
Jiacheng Zhang, Yicong Luo, Zheng En

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9241 - 9251

Опубликована: Март 19, 2024

Much attention has been focused on the catalytic asymmetric creation of single chiral centers or two adjacent stereocenters. However, construction nonadjacent stereocenters is significant importance but challenging because lack remote induction models. Herein, based a C═C bond relay strategy, we report synergistic Pd/Cu-catalyzed 1,5-double model. All four stereoisomers target products bearing 1,5-nonadjacent involving both allenyl axial and central chirality could be obtained divergently by simply changing combination catalysts with different configurations. Control experiments DFT calculations reveal novel mechanism 1,5-oxidative addition, contra-thermodynamic η3-allyl palladium shift, conjugate nucleophilic substitution, which play crucial roles in control reactivity, regio-, enantio-, diastereoselectivity. It expected that this strategy may provide general protocol for synthesis structural motifs distant

Язык: Английский

Процитировано

19
Informing geometric deep learning with electronic interactions to accelerate quantum chemistry DOI Creative Commons
Zhuoran Qiao, Anders S. Christensen, Matthew Welborn

и другие.

Proceedings of the National Academy of Sciences, Год журнала: 2022, Номер 119(31)

Опубликована: Июль 28, 2022

Predicting electronic energies, densities, and related chemical properties can facilitate the discovery of novel catalysts, medicines, battery materials. However, existing machine learning techniques are challenged by scarcity training data when exploring unknown spaces. We overcome this barrier systematically incorporating knowledge molecular structure into deep learning. By developing a physics-inspired equivariant neural network, we introduce method to learn representations based on interactions among atomic orbitals. Our method, OrbNet-Equi, leverages efficient tight-binding simulations learned mappings recover high-fidelity physical quantities. OrbNet-Equi accurately models wide spectrum target while being several orders magnitude faster than density functional theory. Despite only using samples collected from readily available small-molecule libraries, outperforms traditional semiempirical learning-based methods comprehensive downstream benchmarks that encompass diverse main-group processes. also describes in challenging charge-transfer complexes open-shell systems. anticipate strategy presented here will help expand opportunities for studies chemistry materials science, where acquisition experimental or reference is costly.

Язык: Английский

Процитировано

59
Dual Catalysis in Organic Synthesis: Current Challenges and New Trends DOI
Chandi C. Malakar, Luca Dell’Amico, Wanbin Zhang

и другие.

European Journal of Organic Chemistry, Год журнала: 2022, Номер 26(1)

Опубликована: Дек. 9, 2022

Abstract Dual catalysis is one of the most powerful strategies for development chemical reactions in organic synthesis. This strategy can be divided into cooperative catalysis, relay and sequential according to actual mode operation communication between catalysts. In recent years, such has been applied a large number studies since it advantages of: 1) increasing reactivity enabling challenging transformations; 2) offering way controlling stereoselectivity asymmetric reactions, which traditional catalytic systems; 3) catalyze stereodivergent synthesis molecules bearing or more stereocenters from same starting materials. Perspective, intends introduce reader EurJOC special collection on Catalysis , aims summarize different categories dual demonstrate their benefits constructing new bonds selective manner. Finally, current challenges trends will also presented.

Язык: Английский

Процитировано

56
Asymmetric transformations enabled by synergistic dual transition-metal catalysis DOI Creative Commons
Liang Wei, Chun‐Jiang Wang

Chem Catalysis, Год журнала: 2022, Номер 3(1), С. 100455 - 100455

Опубликована: Ноя. 17, 2022

Язык: Английский

Процитировано

55
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

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(10)

Опубликована: Янв. 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.

Язык: Английский

Процитировано

34
Advances and Prospects in Understanding London Dispersion Interactions in Molecular Chemistry DOI Creative Commons
Lars Rummel, Peter R. Schreiner

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(12)

Опубликована: Дек. 5, 2023

London dispersion (LD) interactions are the main contribution of attractive part van der Waals potential. Even though LD effects driving force for molecular aggregation and recognition, role these omnipresent in structure reactivity had been largely underappreciated over decades. However, recent years considerable efforts have made to thoroughly study their potential as a chemical design element structures catalysis. This was possible through fruitful interplay theory experiment. review highlights results advances utilizing structural motif understand utilize intra- intermolecularly LD-stabilized systems. Additionally, we focus on quantification fundamental reactions.

Язык: Английский

Процитировано

28