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

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Axially chiral alkenes: Atroposelective synthesis and applications

Tetrahedron Chem, Год журнала: 2022, Номер 1, С. 100009 - 100009

Опубликована: Март 1, 2022

Axial chirality is historically epitomized by biaryl compounds containing rotationally impeded aryl-aryl linkage. As the field of atroposelective catalysis advances, synthesis and application less common scaffolds such as alkenes have now come to fore. The manifestation axial in aryl was hypothesized 1928 first resolution achieved nearly a decade later. However, catalytic asymmetric construction axially chiral open-chain appeared only 2017 which ushered renewed focus on these structures. In principle, possess an alkene group tethered at one end stereogenic axis, greatly reduces overall rigidity. To date, atropisomers with C (vinyl)-C (aryl) (vinyl)-heteroatom bond been reported. Considering rapid growth synthetic utility alkenes, this review intends provide historical overview discusses new developments. It hope that timely discussion would motivate continued nascent field.

Язык: Английский

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Synthesis of axially chiral alkenylboronates through combined copper- and palladium-catalysed atroposelective arylboration of alkynes

Nature Synthesis, Год журнала: 2023, Номер 2(2), С. 140 - 151

Опубликована: Янв. 5, 2023

Язык: Английский

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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

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Synthetic strategies and mechanistic studies of axially chiral styrenes

Chem Catalysis, Год журнала: 2023, Номер 3(6), С. 100594 - 100594

Опубликована: Апрель 6, 2023

Язык: Английский

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Atroposelective catalysis

Nature Reviews Chemistry, Год журнала: 2024, Номер 8(7), С. 497 - 517

Опубликована: Июнь 18, 2024

Язык: Английский

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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

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Pd^II‐Catalyzed C(alkenyl)−H Activation Facilitated by a Transient Directing Group**

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(25)

Опубликована: Апрель 25, 2022

Palladium(II)-catalyzed C(alkenyl)-H alkenylation enabled by a transient directing group (TDG) strategy is described. The dual catalytic process takes advantage of reversible condensation between an alkenyl aldehyde substrate and amino acid TDG to facilitate coordination the metal catalyst subsequent activation tailored carboxylate base. resulting palladacycle then engages acceptor alkene, furnishing 1,3-diene with high regio- E/Z-selectivity. reaction enables synthesis enantioenriched atropoisomeric 2-aryl-substituted 1,3-dienes, which have seldom been examined in previous literature. Catalytically relevant palladacycles were synthesized characterized X-ray crystallography, energy profiles step stereoinduction model elucidated density functional theory (DFT) calculations.

Язык: Английский

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Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes

ACS Catalysis, Год журнала: 2024, Номер 14(15), С. 11318 - 11331

Опубликована: Июль 15, 2024

Catalytic enantioselective borylation reactions of unsaturated bonds as powerful tools for the synthesis diverse chiral organoboron compounds have gained much attention and wide applications in various fields. However, atroposelective arylboration reaction with carbon–carbon triple 1,3-enynes to obtain axially 1,3-dienylboronates remains an elusive significant challenge. Hence, we develop a cooperative copper- palladium-catalyzed assemble plentiful function enriched single step from easily available 1,3-enynes, B2pin2, aryl bromides high levels chemo-, regio-, stereo-, atroposelectivity. The mild conditions lead good functional group tolerance, which is proven by broad substrate scope late-stage functionalizations bioactive or drug molecules. Moreover, can be scaled up, series further transformations achieved. It worth emphasizing that several olefin catalysts ligands axial chirality also synthesized through corresponding elaborations such products, explains transformative ability application potential 1,3-dienylboronates. mechanism experiment density theory (DFT) calculations revealed process copper palladium catalysis, indicating chemoselectivity regioselectivity boration are determined enyne insertion on copper, atroposelectivity controlled reductive elimination center. Meanwhile, calculation demonstrated distinct interactions between P═O C═O groups Pd Bpin center key transition state formation products varying configurations while employing identical configuration ligands.

Язык: Английский

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1,3-diene-based AIEgens: Stereoselective synthesis and applications

iScience, Год журнала: 2024, Номер 27(3), С. 109223 - 109223

Опубликована: Фев. 15, 2024

SummaryIn recent years, significant advancements have been made in the synthesis and application of 1,3-dienes. This specific structural motif has garnered attention from researchers materials science biology due to its unique aggregation-induced emission (AIE) properties extensive conjugation systems. The luminescent characteristics these compounds are notably influenced by geometry two double bonds. Therefore, it is essential consolidate stereoselective synthetic strategies for comprehensive review seeks elucidate diverse techniques employed attain stereo-control 1,3-diene-based AIE luminogens (AIEgens). Particular emphasis placed on comprehending determinants stereoselectivity exploring array substrates amenable methods. Furthermore, underscores exhibited their utility organic light-emitting diodes (OLEDs), stimuli-responsive materials, sensors, bioimaging, photodynamic therapy (PDT).Graphical abstract

Язык: Английский

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