Ligand-Controlled Regioselective Dearomative Vicinal and Conjugate Hydroboration of Quinolines DOI
Chao Hu,

Chen-Yan Cai,

Elizabeth S. Barta

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 27, 2025

A dearomative strategy to regioselectively modify arenes using a "diene" synthon within aromatic rings provides access highly functionalized heterocycles from abundant feedstocks and represents an alternative synthetic approach besides traditional cross-coupling C-H functionalization methodologies. In this study, we present efficient method for selectively introducing boron onto quinolines through hydroboration easily accessible stable phosphine-ligated borane complexes. The vicinal 5,6- conjugate 5,8-hydroborated products could be obtained by modifying the phosphine ligand. Drawing inspiration diverse organoboron transformations, these building blocks were diversified range of downstream functionalizations, providing modular pathways skeletal modifications variety challenging heterocycles.

Язык: Английский

Photoredox-Enabled Dearomative [2π + 2σ] Cycloaddition of Phenols DOI
Subhabrata Dutta, Donghyeon Lee,

Kristers Ozols

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(4), С. 2789 - 2797

Опубликована: Янв. 18, 2024

Dearomative photocycloaddition of monocyclic arenes is an appealing strategy for comprehending the concept "escape from flatland". This brings replacement readily available planar aromatic hydrocarbon units with a 3D fused bicyclic core sp3-enriched carbon units. Herein, we outline intermolecular approach dearomative phenols. In order to circumvent ground-state aromaticity and construct conformationally restrained building blocks, bicyclo[1.1.0]butanes were chosen as coupling partners. renders straightforward access bicyclo[2.1.1]hexane unit cyclic enone moiety, which further contributed synthetic linchpin postmodifications. Mechanistic experiment advocates plausible onset both reactants, depending on redox potential.

Язык: Английский

Процитировано

66
15NRORC: An Azine Labeling Protocol DOI

Zachary A. Tolchin,

Joel M. Smith

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 2939 - 2943

Опубликована: Янв. 12, 2024

A practical method for the synthesis of 15N-labeled azines with a high degree isotopic enrichment is described. Activation azine heterocycles an electron-deficient arene allows facile substitution nitrogen atom specifically designed reagent that undergoes canonical ANRORC-type mechanism. wide range can be converted to their corresponding 15N isotopologs using this method, and it also dearomative access reduced heterocyclic congeners. short formal 15N-solifenacin accomplished as well demonstrate application generating labeled pharmaceuticals.

Язык: Английский

Процитировано

27
Rhodium-Catalyzed Asymmetric Allylic Dearomatization of β-Naphthols with gem-Difluorinated Cyclopropanes DOI
Ziqi Yang,

Yiliang Gong,

Qing Gu

и другие.

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4287 - 4293

Опубликована: Фев. 25, 2025

Язык: Английский

Процитировано

3
Visible‐Light Promoted Intramolecular para‐Cycloadditions on Simple Aromatics DOI Creative Commons

Maurizio Chiminelli,

Andrea Serafino, Davide Ruggeri

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(12)

Опубликована: Янв. 27, 2023

Abstract Dearomative cycloadditions are a powerful tool to access large chemical space exploiting simple and ubiquitous building blocks. The energetic burden due the loss of aromaticity has however greatly limited their synthetic potential. We devised general intramolecular method that overcomes these limitations thanks photosensitization allenamides. visible‐light‐promoted process gives complex [2.2.2]‐(hetero)‐bicyclooctadienes at room temperature, likely through stabilization transient (bi)radicals by naphthalene. reaction tolerates several valuable functionalities, offering convenient handle for myriad applications, including original isoindoles metal complexes.

Язык: Английский

Процитировано

31
Recent advances in oxidative phenol coupling for the total synthesis of natural products DOI
Matthew C. Carson, Marisa C. Kozlowski

Natural Product Reports, Год журнала: 2023, Номер 41(2), С. 208 - 227

Опубликована: Июнь 9, 2023

Covering: 2008 to 2023This review will describe oxidative phenol coupling as applied in the total synthesis of natural products. This covers catalytic and electrochemical methods with a brief comparison stoichiometric enzymatic systems assessing their practicality, atom economy, other measures. Natural products forged by C-C C-O couplings well from alkenyl be addressed. Additionally, exploration into phenols related species (carbazoles, indoles, aryl ethers,

Язык: Английский

Процитировано

25
Recent Advances in Dearomative Partial Reduction of Benzenoid Arenes DOI

De‐Hai Liu,

Jiajia Ma

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)

Опубликована: Март 14, 2024

Abstract Dearomative partial reduction is an extraordinary approach for transforming benzenoid arenes and has been well‐known many decades, as exemplified by the dehydrogenation of Birch hydroarylation Crich addition. Despite its remarkable importance in synthesis, this field experienced slow progress over last half‐century. However, a revival observed with recent introduction electrochemical photochemical methods. In Minireview, we summarize advancements dearomative arenes, including dihydrogenation, hydroalkylation, arylation, alkenylation, amination, borylation others. Further, intriguing utilization synthesis natural products also emphasized. It anticipated that Minireview will stimulate further arene transformations.

Язык: Английский

Процитировано

15
Photochemical dearomative skeletal modifications of heteroaromatics DOI Creative Commons
Peng Ji, Kuaikuai Duan, Menglong Li

и другие.

Chemical Society Reviews, Год журнала: 2024, Номер 53(12), С. 6600 - 6624

Опубликована: Янв. 1, 2024

Dearomatization has emerged as a powerful tool for rapid construction of 3D molecular architectures from simple, abundant, and planar (hetero)arenes. The field evolved beyond simple dearomatization driven by new synthetic technology development. With the renaissance photocatalysis expansion activation mode, last few years have witnessed impressive developments in innovative photochemical methodologies, enabling skeletal modifications dearomatized structures. They offer truly efficient useful tools facile highly complex structures, which are viable natural product synthesis drug discovery. In this review, we aim to provide mechanistically insightful overview on these innovations based degree alteration, categorized into dearomative functionalization editing, highlight their utilities.

Язык: Английский

Процитировано

14
Dearomatization drives complexity generation in freshwater organic matter DOI Creative Commons
Siyu Li,

Mourad Harir,

David Bastviken

и другие.

Nature, Год журнала: 2024, Номер 628(8009), С. 776 - 781

Опубликована: Апрель 24, 2024

Dissolved organic matter (DOM) is one of the most complex, dynamic and abundant sources carbon, but its chemical reactivity remains uncertain

Язык: Английский

Процитировано

13
Gd(III)-Catalyzed Regio-, Diastereo-, and Enantioselective [4 + 2] Photocycloaddition of Naphthalene Derivatives DOI
Muzi Li,

Xu‐Lun Huang,

Zuo‐Yu Zhang

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(25), С. 16982 - 16989

Опубликована: Июнь 13, 2024

Catalytic asymmetric dearomatization (CADA) reactions have evolved into an efficient strategy for accessing chiral polycyclic and spirocyclic scaffolds from readily available planar aromatics. Despite the significant developments, CADA reaction of naphthalenes remains underdeveloped. Herein, we report a Gd(III)-catalyzed naphthalene with PyBox ligand via visible-light-enabled [4 + 2] cycloaddition. This features application Gd/PyBox complex, which regulates reactivity selectivity simultaneously, in excited-state catalysis. A wide range functional groups is compatible this protocol, giving highly enantioenriched bridged polycycles excellent yields (up to 96%) >20:1 chemoselectivity, dr, >99% ee). The synthetic utility demonstrated by 2 mmol scale reaction, removal directing group, diversifications products. Preliminary mechanistic experiments are performed elucidate mechanism.

Язык: Английский

Процитировано

11
Photo-induced intramolecular dearomative [5 + 4] cycloaddition of arenes for the construction of highly strained medium-sized-rings DOI Creative Commons
Min Zhu, Yuanjun Gao,

Xu‐Lun Huang

и другие.

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

Опубликована: Март 19, 2024

Abstract Medium-sized-ring compounds have been recognized as challenging synthetic targets in organic chemistry. Especially, the difficulty of synthesis will be augmented if an E -olefin moiety is embedded. Recently, photo-induced dearomative cycloaddition reactions that proceed via energy transfer mechanism witnessed significant developments and provided powerful methods for transformations are not easily realized under thermal conditions. Herein, we report intramolecular [5 + 4] naphthalene-derived vinylcyclopropanes visible-light irradiation a proper triplet photosensitizer. The reaction affords dearomatized polycyclic molecules possessing nine-membered-ring with good yields (up to 86%) stereoselectivity 8.8/1 / Z ). Detailed computational studies reveal origin behind favorable formation thermodynamically less stable isomers. Diverse derivations products also demonstrated.

Язык: Английский

Процитировано

10