Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

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

---

Atroposelective Synthesis of Conjugated Diene-Based Axially Chiral Styrenes via Pd(II)-Catalyzed Thioether-Directed Alkenyl C–H Olefination

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

---

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

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

---

Stereoselective Synthesis of C‐Vinyl Glycosides via Palladium‐Catalyzed C−H Glycosylation of Alkenes

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

---

Transition‐Metal‐Catalyzed Annulations Involving the Activation of C(sp³)−H Bonds

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

Опубликована: Окт. 26, 2021

The selective functionalization of C(sp

Язык: Английский

---

Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

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

---

Simple Ether‐Directed Enantioselective C(sp³)−H Borylation of Cyclopropanes Enabled by Iridium Catalysis

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

---

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

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

---

Organocatalytic olefin C–H functionalization for enantioselective synthesis of atropisomeric 1,3-dienes

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

Опубликована: Янв. 17, 2024

Язык: Английский

---

Olefination via Cu-Mediated Dehydroacylation of Unstrained Ketones

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(48), С. 20042 - 20048

Опубликована: Ноя. 22, 2021

The dehydroacylation of ketones to olefins is realized under mild conditions, which exhibits a unique reaction pathway involving aromatization-driven C-C cleavage remove the acyl moiety, followed by Cu-mediated oxidative elimination form an alkene between α and β carbons. newly adopted N'-methylpicolinohydrazonamide (MPHA) reagent key enable efficient ketone bonds at room temperature. Diverse alkyl- aryl-substituted olefins, dienes, special alkenes are generated with broad functional group tolerance. Strategic applications this method also demonstrated.

Язык: Английский

---