Rhenium-Catalyzed C(sp2)–H Silylalkenylation of Arenes: An Anti-Markovnikov Linchpin Strategy DOI
Suman Bhowmick,

Annapurna Awasthi,

Khushboo Tiwari

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 28, 2025

Re-catalyzed highly regio- and stereoselective o-C(sp2)–H silylalkenylation of arenes is reported using a directing group approach under ligand-, additive-, base-free conditions. A series imine groups (DGs) have been exploited on aromatic aldehydes to overcome de novo synthesis. This unique protocol allows us access o-C–H activation various heterocyclic moieties, including N-aryl 2-pyridones arylpyridines. Sequential difunctionalization experiments performed. mechanistic carried out gain insight.

Язык: Английский

Efficient Synthesis of Sulfur-Stereogenic Sulfoximines via Ru(II)-Catalyzed Enantioselective C–H Functionalization Enabled by Chiral Carboxylic Acid DOI
Tao Zhou, Pu‐Fan Qian, Jun-Yi Li

и другие.

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(18), С. 6810 - 6816

Опубликована: Апрель 28, 2021

Ru(II)-catalyzed enantioselective C-H functionalization involving an enantiodetermining cleavage step remains undeveloped. Here we describe a activation/annulation of sulfoximines with α-carbonyl sulfoxonium ylides using novel class chiral binaphthyl monocarboxylic acids as ligands, which can be easily and modularly prepared from 1,1'-binaphthyl-2,2'-dicarboxylic acid. A broad range sulfur-stereogenic were in high yields excellent enantioselectivities (up to 99% yield ee) via desymmetrization, kinetic resolution, parallel resolution. Furthermore, the resolution products transformed sulfoxides key intermediates for kinase inhibitors.

Язык: Английский

Процитировано

168

Recent Advances in Alkenyl sp2 C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications DOI
Mingzhu Lu, Jeffrey Goh, Manikantha Maraswami

и другие.

Chemical Reviews, Год журнала: 2022, Номер 122(24), С. 17479 - 17646

Опубликована: Окт. 14, 2022

Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, advanced materials. Significant efforts have been made toward the development new practical methods to access this important class compounds by selectively activating alkenyl C(sp2)–H bonds recent years. In comprehensive review, we describe state-of-the-art strategies for direct functionalization sp2 C–H C–F until June 2022. Moreover, metal-free, photoredox, electrochemical also covered. For clarity, review has divided into two parts; first part focuses on currently available using different alkene as starting materials, second describes bond easily accessible gem-difluoroalkenes material. This includes scope, limitations, mechanistic studies, stereoselective control (using directing groups well metal-migration strategies), applications complex molecule synthesis where appropriate. Overall, aims document considerable advancements, current status, emerging work critically summarizing contributions researchers working fascinating area is expected stimulate novel, innovative, broadly applicable functionalizations coming

Язык: Английский

Процитировано

155

Stereoselective construction of atropisomers featuring a C–N chiral axis DOI Creative Commons

Yong‐Jie Wu,

Gang Liao, Bing‐Feng Shi

и другие.

Green Synthesis and Catalysis, Год журнала: 2022, Номер 3(2), С. 117 - 136

Опубликована: Янв. 4, 2022

Atropisomeric C–N compounds belong to an important class of axially chiral compounds. However, whereas the asymmetric synthesis biaryl atropisomers have been well established, general and efficient strategies access single enantiomers are still rare. Until recently, innovative methods developed, providing new opportunities for highly stereoselective this vital atropisomers. Herein, we comprehensively summarize development in emerging field give some insights into future advance. Emphasis is placed on synthetic strategies.

Язык: Английский

Процитировано

151

Forging C−heteroatom bonds by transition-metal-catalyzed enantioselective C–H functionalization DOI Creative Commons
Qi Zhang,

Le‐Song Wu,

Bing‐Feng Shi

и другие.

Chem, Год журнала: 2021, Номер 8(2), С. 384 - 413

Опубликована: Дек. 17, 2021

Язык: Английский

Процитировано

122

Cobalt(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective Synthesis of Benzothiadiazine‐1‐oxides via C−H Activation DOI
Yuuki Hirata,

Daichi Sekine,

Yoshimi Kato

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(28)

Опубликована: Май 2, 2022

Abstract Among sulfoximine derivatives containing a chiral sulfur center, benzothiadiazine‐1‐oxides are important for applications in medicinal chemistry. Here, we report that the combination of an achiral cobalt(III) catalyst and pseudo‐ C 2 ‐symmetric H 8 ‐binaphthyl carboxylic acid enables asymmetric synthesis from sulfoximines dioxazolones via enantioselective C−H bond cleavage. With optimized protocol, with several functional groups can be accessed high enantioselectivity.

Язык: Английский

Процитировано

74

Enantioselective Synthesis of N‐N Atropisomers by Palladium‐Catalyzed C−H Functionalization of Pyrroles DOI
Yao Wang, Chuan‐Jun Lu,

Li‐Wen Zhan

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(21)

Опубликована: Март 21, 2023

The catalytic asymmetric construction of N-N atropisomeric biaryls remains a formidable challenge. Studies them lag far behind studies the more classical carbon-carbon biaryl atropisomers, hampering meaningful development. Herein, first palladium-catalyzed enantioselective C-H activation pyrroles for synthesis atropisomers is presented. Structurally diverse indole-pyrrole possessing chiral axis were produced with good yields and high enantioselectivities by alkenylation, alkynylation, allylation, or arylation reactions. Furthermore, kinetic resolution trisubstituted heterobiaryls sterically demanding substituents was also achieved. Importantly, this versatile functionalization strategy enables iterative exquisite selectivity, expediting formation valuable, complex, atropisomers.

Язык: Английский

Процитировано

55

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

Cobalt-Catalyzed Enantioselective C–H Annulation with Alkenes DOI
Dandan Yang, Xian Zhang, Xinghua Wang

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(7), С. 4250 - 4260

Опубликована: Март 13, 2023

Herein, we disclose an efficient cobalt-catalyzed enantioselective C–H activation and annulation of benzamides with alkenes. This transformation is facilitated via the commercially available cobalt(II) catalyst in presence easily prepared chiral salicyl-oxazoline (Salox) ligand, which provides facile access to (R) or (S) enantiomers dihydroisoquinolone derivatives. It noticeable that reaction proceeded efficiently within extremely short time from 10 30 min under mild conditions. A broad range alkenes bear various functional substituents have been shown good compatibility deliver targeted products high yields enantioselectivities (51 examples, up 98% yield 99% ee). The gram scale experiment removal directing group further demonstrate practicability this protocol potential industrial applications. Density theory calculations elucidate mechanism, spin-state change olefin insertion step accelerates subsequent C–N reductive elimination, identified as stereo-determining step. AIM analysis indicates π interactions are vital for controlling switching stereoselectivity.

Язык: Английский

Процитировано

45

Enantioselective and Diastereoselective C–H Alkylation of Benzamides: Synergized Axial and Central Chirality via a Single Stereodetermining Step DOI
Jinlei Wang, Haohua Chen,

Lingheng Kong

и другие.

ACS Catalysis, Год журнала: 2021, Номер 11(15), С. 9151 - 9158

Опубликована: Июль 9, 2021

In this report, distally disposed axial and central chirality has been installed in a synergistic fashion via rhodium-catalyzed C–H alkylation of benzamides using N-arylmaleimide as the alkylating reagent, which enantio- diastereo-determining steps are merged into single one. The coupling system features mild reaction conditions, broad substrate scope, excellent diastereoselectivity. chiral induction enabled by judicious choice rhodium cyclopentadienyl catalyst that serves to control both orientation olefin unit prochiral C–N bond.

Язык: Английский

Процитировано

65

Highly Atroposelective Rhodium(II)-Catalyzed N–H Bond Insertion: Access to Axially Chiral N-Arylindolocarbazoles DOI
Qiao Ren, Tingting Cao, Chun‐Nian He

и другие.

ACS Catalysis, Год журнала: 2021, Номер 11(10), С. 6135 - 6140

Опубликована: Май 6, 2021

The highly atroposelective construction of axially chiral N-arylindolocarbazoles is disclosed via the Rh(II)-catalyzed intermolecular carbene N–H insertion reactions. This straightforward transformation provides a rapid access to wide range enantio-enriched N-arylindolocarbazole atropisomers bearing C–N axis in moderate good yields and high enantioselectivities. Also, synthetic utility this protocol unambiguously emphasized by late-stage functionalization (LSF) some representative natural products bioactive molecules. Furthermore, polyaromatic ring N-arylindolocarbazole-derived phosphoric acid (CPA) synthesis also highlight its practical value materials chemistry catalytic asymmetric synthesis.

Язык: Английский

Процитировано

62