Chemo-, Regio-, and Stereoselective Assembly of Polysubstituted Furan-2(5H)-ones Enabled by Rh(III)-Catalyzed Domino C–H Alkenylation/Directing Group Migration/Lactonization: A Combined Experimental and Computational Study DOI
Fei Zhao, Zhi Zhou, Yangbin Lu

и другие.

ACS Catalysis, Год журнала: 2021, Номер 11(22), С. 13921 - 13934

Опубликована: Ноя. 2, 2021

Exploring multistep cascade reactions triggered by C–H activation are recognized as appealing, yet challenging. Herein, we disclose a Rh(III)-catalyzed domino coupling of N-carbamoyl indoles and 4-hydroxy-2-alkynoates for the streamlined assembly highly functionalized furan-2(5H)-ones in which carbamoyl-directing group (DG) is given dual role an auxiliary migrating acylating reagent via cleavage stable C–N bonds at room temperature. More importantly, obtained furan-2(5H)-one skeleton could be further under air situ C5–H hydroxylation simply switching solvent or additive, providing fully substituted with installation alcohol-based C5 quaternary carbon center. Detailed experimental studies density functional theory calculations reveal that Rh(III)-mediated tandem activation/alkyne insertion/DG migration/lactonization accounts developed transformation to achieve high functionalities observed exclusive selectivity. The potential biological application class potent PPARγ ligands highlights synthetic utility methodology. This protocol endowed several salient features including efficient activation, excellent chemo-, regio-, stereoselectivity, bond-forming efficiency (e.g., two C–C C–O bonds), solvent- additive-controlled product selectivity, good functional-group compatibility, mild redox-neutral conditions.

Язык: Английский

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

Atroposelective Synthesis of Conjugated Diene-Based Axially Chiral Styrenes via Pd(II)-Catalyzed Thioether-Directed Alkenyl C–H Olefination DOI
Liang Jin, Peng Zhang, Ya Li

и другие.

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(31), С. 12335 - 12344

Опубликована: Авг. 3, 2021

The efficient stereoselective synthesis of conjugated dienes, especially those with axial chirality, remains a great challenge. Herein, we report the highly atroposelective axially chiral styrenes 1,3-diene scaffold via Pd(II)-catalyzed thioether-directed alkenyl C-H olefination strategy. This strategy features easy operation, mild reaction conditions, high functional group tolerance (69 examples), complete Z-selectivity, and excellent enantioselectivities (up to 99% ee). Notably, enantioselective atropisomers two stereogenic axes were also achieved using this ee 97:3 dr). Moreover, could be scaled up, resulting easily oxidized into sulfoxide derivatives diastereoselectivities, which showed promise as new type sulfur-olefin ligand.

Язык: Английский

Процитировано

125

Recent advances in catalytic asymmetric alkenyl C(sp2)–H bond functionalizations DOI Creative Commons

Xiao‐Ju Si,

Tian-Ci Wang,

Teck‐Peng Loh

и другие.

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review summarizes recent advances in asymmetric alkenyl C–H bond functionalization reactions, as well provides an outlook on future opportunities and challenges.

Язык: Английский

Процитировано

3

Stereoselective Synthesis of C‐Vinyl Glycosides via Palladium‐Catalyzed C−H Glycosylation of Alkenes DOI
Qikai Sun, Huixing Zhang,

Quanquan Wang

и другие.

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(36), С. 19620 - 19625

Опубликована: Июль 6, 2021

C-vinyl glycosides are an important class of carbohydrates and pose a unique synthetic challenge. A new strategy has been developed for stereoselective synthesis via Pd-catalyzed directed C-H glycosylation alkenes with glycosyl chloride donors using easily removable bidentate auxiliary. Both the γ bond allylamines δ homoallyl amine substrates can be glycosylated in high efficiency excellent regio- stereoselectivity. The resulting further converted to variety C-alkyl stereospecificity. These reactions offer broadly applicable method streamline complex from accessible starting materials.

Язык: Английский

Процитировано

70

Transition‐Metal‐Catalyzed Annulations Involving the Activation of C(sp3)−H Bonds DOI
Marc Font, Moisés Gulı́as, José L. Mascareñas

и другие.

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(6)

Опубликована: Окт. 26, 2021

The selective functionalization of C(sp

Язык: Английский

Процитировано

66

Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes DOI
Pu‐Fan Qian, Tao Zhou, Bing‐Feng Shi

и другие.

Chemical Communications, Год журнала: 2023, Номер 59(85), С. 12669 - 12684

Опубликована: Янв. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Язык: Английский

Процитировано

43

Simple Ether‐Directed Enantioselective C(sp3)−H Borylation of Cyclopropanes Enabled by Iridium Catalysis DOI Open Access
Tian Xie, Lili Chen, Zhenlu Shen

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(14)

Опубликована: Фев. 10, 2023

Reported here is an efficient and simple ether-directed iridium-catalyzed enantioselective C(sp3 )-H borylation of cyclopropanes. Various functional groups were well-tolerated, affording a vast array chiral cyclopropanes with high enantioselectivities. We also demonstrated that the turnover numbers current reaction could be up to 335.

Язык: Английский

Процитировано

28

Coordination Assistance: A Powerful Strategy for Metal-Catalyzed Regio- and Enantioselective Hydroalkynylation of Internal Alkenes DOI
Wei Zhao,

Hou‐Xiang Lu,

Wenwen Zhang

и другие.

Accounts of Chemical Research, Год журнала: 2023, Номер 56(3), С. 308 - 321

Опубликована: Янв. 11, 2023

ConspectusAlkenes are versatile compounds that readily available on a large scale from industry or through organic synthesis. The widespread occurrence of alkenes provides the continuous impetus for development catalytic asymmetric alkene hydrofunctionalizations, which enables expeditious construction complex chiral molecules starting materials. Catalytic hydrofunctionalization internal presents notable challenge, due to their low reactivity, many potential side reactions, and simultaneous control regio-, diastereo-, enantioselectivities.Dehydroamino acids enamides among first substrates provide enantioselectivities in hydrogenation. crucial importance an amide coordinating group is established by series classical mechanistic studies. This initial success greatly stimulated further hydrogenation hydrofunctionalization. Building these pioneering works as well related we have adopted coordination assistance powerful tool address challenges associated with alkenes. Using functional substrate native group, two-point binding mode metal center effectively enhances reactivity facilitates diastereo- enantioselectivities. Through this strategy, developed number methods excellent enantiocontrols.In Account, summarize recent advance our lab using key element achieve regio- enantioselective hydroalkynylation First, describe early work aimed at controlling enantioselectivity disubstituted enamide substrate. Both α- β-alkynylation were achieved channeling reaction pathway into Chalk-Harrod modified mechanism. Next, discuss catalysts regiodivergent trisubstituted access vicinal stereocenters quaternary carbon stereocenters. We also α,β-unsaturated amides unconventional site-selectivity combination isomerization regioselective hydroalkynylation. basis remote stereocenter β,γ-unsaturated amides. show principle applicable terminal well. A ligand-controlled mechanism shift discussed alkynylation position 1,1,-disubstituted Finally, briefly mention application other hydrofunctionalizations such hydroboration hydrosilylation, where previously inaccessible selectivity achieved. Collectively, demonstrate power hydrofunctionalizations. anticipate strategy will create platform enable diverse transformations.

Язык: Английский

Процитировано

26

Organocatalytic olefin C–H functionalization for enantioselective synthesis of atropisomeric 1,3-dienes DOI
Quan‐Hao Wu, Meng Duan, Yu Chen

и другие.

Nature Catalysis, Год журнала: 2024, Номер 7(2), С. 185 - 194

Опубликована: Янв. 17, 2024

Язык: Английский

Процитировано

14

Metal incorporated sulfonamides as promising multidrug targets: Combined enzyme inhibitory, antimicrobial, antioxidant and theoretical exploration DOI
Sajjad Hussain Sumrra,

Abrar U. Hassan,

Muhammad Nadeem Zafar

и другие.

Journal of Molecular Structure, Год журнала: 2021, Номер 1250, С. 131710 - 131710

Опубликована: Окт. 18, 2021

Язык: Английский

Процитировано

47