Chem, Journal Year: 2024, Volume and Issue: 10(12), P. 3529 - 3531
Published: Dec. 1, 2024
Language: Английский
ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 1294 - 1304
Published: Jan. 7, 2025
Given the widespread presence of spirocyclic scaffolds in natural products and pharmacologically relevant synthetic compounds, development efficient methodologies for their construction holds great importance medicinal chemistry pharmaceutical research. In this study, a general photochemical dearomative spirocyclization nonactivated arenes has been established. The key to method lies ability amine-borane radicals activate aryl bromides iodides via halogen-atom transfer, thereby allowing conversion halides into corresponding subsequent chemodivergent transformations. remarkable compatibility versatility 1,4-difunctionalization is showed by rapid assembly structurally diverse 1,4-cyclohexadiene-based spirocycles incorporating oxindole, indoline, or dihydrobenzofuran subunits. Moreover, potential utility protocol exemplified formal total synthesis vasopressin V2 receptor antagonist Satavaptan.
Language: Английский
Citations
1
Science, Journal Year: 2025, Volume and Issue: 387(6739), P. 1167 - 1174
Published: March 13, 2025
The ozonolytic deconstruction of aromatics remains a challenge in organic chemistry. Ozone preferentially reacts with alkenes over arenes, meaning that once the initial aromatic cleavage occurs, dearomatized products are inherently more reactive than starting materials. Consequently, process cannot be halted, resulting full oxidation. Addressing this requires subverting intrinsic rules chemoselectivity to transform less substrate presence one. We demonstrate concept can achieved by using photoexcited nitroarenes. Crucial success chemoselective is use nitroarene excitable triplet π,π* state n,π* state. This switch excited-state configuration provides an otherwise inaccessible manifold, which oxidative diverted toward alkenes.
Language: Английский
Citations
1
Chemical Science, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 1, 2025
Radical-mediated dearomatization strategies offer a blueprint for building value-added and synthetically valuable three-dimensional skeletons from readily available aromatic starting materials.
Language: Английский
Citations
0
The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown
Published: Feb. 13, 2025
A Tf2O-triggered dearomative triazinylmethylation of isoquinolines and other azaarenes utilizing acetonitrile as the nucleophile has been developed through a formal five-component reaction. This method showcases broad substrate scope exceptional functional group compatibility, presenting mild expedient synthetic approach. Kinetic studies, including kinetic isotope effect (KIE) Hammett analysis, indicate that activation by Tf2O constitutes rate-limiting step.
Language: Английский
Citations
0
Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown
Published: March 11, 2025
ConspectusDearomatization of simple aromatics serves as one the most direct strategies for converting abundant chemical feedstocks into three-dimensional value-added products. Among such transformations, cycloadditions between arenes and alkenes have historically offered effective means to construct complex polycyclic architectures. However, traditionally harsh conditions, high-energy UV light irradiation, greatly limited scope this transformation. Nevertheless, recent progress has led development visible-light-promoted dearomative photocycloadditions with expanded capable preparing bicyclic structures.A fundamentally distinct approach involves visible-light activation arenophiles, which undergo para-photocycloaddition various aromatic compounds produce arene-arenophile cycloadducts. While only transiently stable subject retro-cycloaddition, further functionalization photocycloadducts allowed a wide collection dearomatization methodologies that access products orthogonal existing biological processes. Central strategy was observation photocycloaddition reveals π-system can be functionalized through traditional olefin chemistry. Coupled subsequent [4 + 2]-cycloreversion arenophile, process acts effectively isolate single from an ring. We developed several transformations bias methodology perform single-atom insertion π-extension reactions prepare unique cannot prepared easily means.Through application epoxidation, we were able develop method epoxidation pyridines arene-oxides pyridine-oxides, respectively. Notably, when arenophile chemistry is applied arenes, transposed site native olefinic reactivity, enabling site-selectivity functionalization. As result, oxygen (aza)arenes 3-benzoxepines. When applying in context cyclopropanations, accomplish cyclopropanation yield benzocycloheptatrienes upon cycloreversion. while Buchner ring expansion powerful carbon corresponding does not ring-expanded Furthermore, could utilized synthesis novel nanographenes M-region annulative (M-APEX) reaction. Traditionally, methods rely on reactivity at K- bay-region. arenophiles activate reactivity. arenophile-mediated diarylation, followed by cycloreversion, deliver π-extended exclusive selectivity.
Language: Английский
Citations
0
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: March 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.
Language: Английский
Citations
0
Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)
Published: April 16, 2025
Abstract Aromatic compounds serve as key feedstocks in the chemical industry, typically undergoing functionalization or full reduction. However, partial reduction via dearomative sequences remains underexplored despite its potential to rapidly generate complex three-dimensional scaffolds and existing strategies often require metal-mediated multistep processes suffer from limited applicability. Herein, a photocatalytic radical cascade approach enabling difunctionalization through selective spirocyclization/imination of nonactivated arenes is reported. The method employs bifunctional oxime esters carbonates introduce multiple functional groups single step, forming spirocyclic motifs iminyl functionalities N–O bond cleavage, hydrogen-atom transfer, addition, spirocyclization, radical-radical cross-coupling. reaction constructs up four bonds (C−O, C−C, C−N) simple starting materials. Its broad applicability demonstrated on various substrates, including pharmaceuticals, it compatible with scale-up under flow conditions, offering streamlined synthesizing highly decorated frameworks.
Language: Английский
Citations
0
Chem, Journal Year: 2024, Volume and Issue: unknown
Published: Nov. 1, 2024
Language: Английский
Citations
3
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: Nov. 22, 2024
Language: Английский
Citations
2
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown
Published: Dec. 4, 2024
The reduction of abundant benzene rings to scarce C(sp3)-rich motifs is invaluable for drug design, as C(sp3) content known correlate with clinical success. Cyclohexenes are attractive targets, they can be rapidly elaborated into large product libraries and stable against rearomatization. However, partial reactions benzenes cyclohexenes rare have a very narrow scope. Herein we report broadly applicable method that converts electron-poor tolerates Lewis-basic functional groups such triazoles thioethers well reducible cyanides, alkynes, sulfones. reaction utilizes an organic donor induces mild arene by preassociation photoexcitable electron donor–acceptor (EDA) complex isomerization redox-inert 1,4-cyclohexadienes 1,3-cyclohexadienes without strong base in its oxidized thioquinone methide form.
Language: Английский
Citations
1