Introduction DOI
Mohamed S. H. Salem, Shinobu Takizawa

Опубликована: Окт. 18, 2024

Atropisomerism, arising from hindered rotation about single bonds, is a crucial element of molecular chirality with far-reaching implications across scientific disciplines. This opening chapter elucidates the foundational concepts underpinning atropisomerism and chirality, laying groundwork for subsequent discussions. Furthermore, it outlines diverse atroposelective synthetic methodologies, encompassing metal-based organocatalytic oxidative coupling, cross-coupling, ring-opening reactions, which receive detailed consideration in chapters, thus underscoring breadth research this domain. Recent advancements field are highlighted, underlining growing recognition atropisomerism's multifaceted applications. Additionally, addresses persistent challenges impeding further control synthesis, along its expanding applications drug industry development.

Язык: Английский

Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage DOI
Casey B. Roos, Chang-Hwa Chiang, Lauren A. M. Murray

и другие.

Chemical Reviews, Год журнала: 2023, Номер 123(17), С. 10641 - 10727

Опубликована: Авг. 28, 2023

Enantiomers, where chirality arises from restricted rotation around a single bond, are atropisomers. Due to the unique nature of origins their chirality, synthetic strategies access these compounds in an enantioselective manner differ those used prepare enantioenriched containing point arising unsymmetrically substituted carbon center. In particular stereodynamic transformations, such as dynamic kinetic resolutions, thermodynamic and deracemizations, which rely on ability racemize or interconvert enantiomers, promising set transformations optically pure late stage sequence. Translation approaches with atropisomers requires expanded toolbox for epimerization/racemization provides opportunity develop new conceptual framework synthesis compounds.

Язык: Английский

Процитировано

53

Amide C–N bonds activation by A new variant of bifunctional N-heterocyclic carbene DOI Creative Commons

Yuxing Cai,

Yuxin Zhao,

Kai Tang

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Янв. 12, 2024

Abstract We report an organocatalyst that combines a triazolium N-heterocyclic carbene (NHC) with squaramide as hydrogen-bonding donor (HBD), which can effectively catalyze the atroposelective ring-opening of biaryl lactams via unique amide C–N bond cleavage mode. The free species attacks carbonyl, forming axially chiral acyl-azolium intermediate. Various amines be accessed by this methodology up to 99% ee and yield. By using mercaptan catalyst turnover agent, resulting thioester synthon transformed into several interesting atropisomers. Both control experiments theoretical calculations reveal crucial role hybrid NHC-HBD skeleton, activates H-bonding brings it spatially close centre. This discovery illustrates potential chimera demonstrates complementary strategy for activation manipulation.

Язык: Английский

Процитировано

19

Developing Biarylhemiboronic Esters for Biaryl Atropisomer Synthesis via Dynamic Kinetic Atroposelective Suzuki–Miyaura Cross-Coupling DOI

Yiming Yang,

Changhui Wu,

Junhao Xing

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(9), С. 6283 - 6293

Опубликована: Фев. 21, 2024

We herein introduce biarylhemiboronic esters as a new type of bridged biaryl reagent for asymmetric synthesis axially chiral structures, and the palladium-catalyzed Suzuki-Miyaura cross-coupling is developed. This dynamic kinetic atroposelective coupling reaction exhibits high enantioselectivity, good functional group tolerance, broad substrate scope. The synthetic application current method was demonstrated by transformations product programmed polyarene. Preliminary mechanistic studies suggested that proceeded via an enantio-determining transmetalation step.

Язык: Английский

Процитировано

18

Organocatalytic Atroposelective Dynamic Kinetic Resolution Involving Ring Manipulations DOI

Qin Shi,

Fang Fang, Dao‐Juan Cheng

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(6), С. 1269 - 1284

Опубликована: Янв. 31, 2024

Abstract Axially chiral architectures exist widely in natural products, biologically relevant molecules, ligands and catalysts as well functional materials. Therefore, catalytic asymmetric synthesis of atropisomers has become one the most fast‐growing fields community chemistry rapid advances have occurred. Among different methods reported, organocatalytic atroposelective dynamic kinetic resolution (DKR) involving ring manipulations stands out a cutting‐edge technology to construct axial chirality from point atom/step economy. In this DKR strategy, configurational lability starting materials originates chirally‐labile structure cyclic substrates/intermediates or transient formation through noncovalent interactions acyclic substrates. The two material are equilibrium reaction medium, ensuring constant transformation less reactive atropisomer into more one, then single enantiopure product presence an appropriate organocatalyst. This review summarizes recent advancements on topic, including their scopes, limitations, mechanisms, applications provides some insights further developments.

Язык: Английский

Процитировано

11

Catalytic Atroposelective Synthesis of Axially Chiral Heterobiaryl Oxime Ethers via the One-Step Dynamic Kinetic Condensation Reaction DOI

Qianqian Xu,

Jifan Jia,

Haitong Fan

и другие.

Organic Letters, Год журнала: 2024, Номер 26(12), С. 2403 - 2408

Опубликована: Март 19, 2024

The catalytic atroposelective synthesis of axially chiral heterobiaryls was first developed through the direct one-step dynamic kinetic condensation reaction with simple transformation C═O bond to C═N bond, delivering a series novel heterobiaryl oxime ethers.

Язык: Английский

Процитировано

8

Chiral Phosphoric Acid Catalyzed Asymmetric Hydrolysis of Biaryl Oxazepines for the Synthesis of Axially Chiral Biaryl Amino Phenol Derivatives DOI

Liwen Wei,

Jiaomeng Li, Yi Zhao

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(39)

Опубликована: Июнь 20, 2023

The development of catalytic asymmetric reaction with water as the reactant is challenging due to reactivity- and stereoselectivity-control issues resulted from low nucleophilicity small size water. We disclose herein a chiral phosphoric acid (CPA) catalyzed atroposelective ring-opening biaryl oxazepines A series undergo CPA hydrolysis in highly enantioselective manner. key for success this use new SPINOL-derived catalyst high reactivity oxazepine substrates towards under acidic conditions. Density functional theory calculations suggest that proceeds via dynamic kinetic resolution pathway addition imine group both enantio- rate-determining.

Язык: Английский

Процитировано

15

Development of Configurationally Labile Biaryl Reagents for Atropisomer Synthesis DOI
Changhui Wu, Jin Yang, Xiaoyuan Zhang

и другие.

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(28)

Опубликована: Май 16, 2024

Abstract Axially chiral biaryl scaffolds are important in pharmaceuticals, natural products, and asymmetric synthesis. Atroposelective ring‐opening of configurationally labile reagents via dynamic kinetic transformation provides a valuable approach to access axially atropisomers. This review summarizes seminal contributions recent advancements on this topic based the use different types reagents.

Язык: Английский

Процитировано

6

Carbene-Catalyzed Direct O-Functionalization of Ketone: Atroposelective Access to Non-C2-Symmetric Binaphthyls DOI
Bivas Mondal, Hang Chen,

Rakesh Maiti

и другие.

Organic Letters, Год журнала: 2023, Номер 25(46), С. 8252 - 8257

Опубликована: Ноя. 13, 2023

Disclosed here is NHC-catalyzed direct intermolecular trapping of the ketone oxygen atom with acyl azolium intermediate. The overall reaction a dynamic kinetic resolution process that converts to corresponding enol ester well-controlled axial chirality. Our eventually affords non-C2-symmetric binaphthyl derivatives important applications, such as in area asymmetric catalysis.

Язык: Английский

Процитировано

11

Stable Axially Chiral Cyclohexylidenes from Catalytic Asymmetric Knoevenagel Condensation DOI

Meijia Ying,

Kaixuan Wang,

Wenjun Yan

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер 30(39)

Опубликована: Май 7, 2024

Axially chiral cycloalkylidenes are interesting but less developed axially molecules. Here, a bispidine-based amine catalytic system was to promote efficiently the asymmetric Knoevenagel condensation of N-protected oxindoles and benzofuranones with 4-substituted cyclohexanones. A variety alkylidenecycloalkanes stable axial chirality were obtained in good yields fairly er (enantiomeric ratio). Based on absolute configuration determination product DFT calculations, possible mechanism stereoselective induction proposed.

Язык: Английский

Процитировано

4

An Aqueous Three‐Component Reaction of Cyclopropanols, DABCO ⋅ (SO2)2 and Diaryliodonium salts DOI

Yanjie Qiu,

Jiating Yao,

Hongguang Xia

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(19), С. 3392 - 3396

Опубликована: Сен. 14, 2023

Abstract An additive‐ and external oxidant‐free reaction of cyclopropanols, DABCO ⋅ (SO 2 ) diaryliodonium salts in aqueous phase is described. This proceeds under mild conditions, affording bioactive aryl substituted γ‐keto sulfones 36%‐90% yields with good functional group tolerance. through a sulfinate intermediate, which undergoes nucleophilic salts, giving rise to corresponding sulfones.

Язык: Английский

Процитировано

9