Copper‐Catalyzed Oxygenative Skeletal Rearrangement of Tetrahydro‐β‐carbolines Using H2O and O2 as Oxygen Sources DOI Open Access

Yusheng Peng,

Wei Wang, Jun Shi

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(51)

Опубликована: Ноя. 11, 2023

Abstract Herein, we report an unprecedented skeletal rearrangement reaction of tetrahydro‐ β ‐carbolines enabled by copper‐catalyzed single‐electron oxidative oxygenation, in which H 2 O and act as oxygen sources to generate a unique 2‐hydroxyl‐3‐peroxide indoline intermediate. The synthetic reactivity species was demonstrated multi‐step bond cleavage formation cascade. Using readily available copper catalyst under open‐air conditions, highly important yet synthetically difficult spiro[pyrrolidone‐(3,1‐benzoxazine)] products were obtained single operation. utility this methodology is the efficient synthesis natural donaxanine chimonamidine, well 3‐hydroxyl‐pyrroloindoline scaffold, just one or two steps.

Язык: Английский

Visible-Light Photoredox-Catalyzed Intermolecular α-Aminomethyl/Carboxylative Dearomatization of Indoles with CO2 and α-Aminoalkyl Radical Precursors DOI

Wanxu Gao,

Qi Yang,

Yang Han

и другие.

Organic Letters, Год журнала: 2024, Номер 26(2), С. 467 - 472

Опубликована: Янв. 5, 2024

Disclosed here is a visible-light photoredox-catalyzed intermolecular sequential α-aminomethyl/carboxylative dearomatization of indoles with CO2 and α-aminoalkyl radical precursors, affording series functionalized indoline-3-carboxylic acids lactams in good yields high regioselectivity. This multicomponent reaction provides green facile method for the synthesis diverse indolines by using as carboxylic carbonyl source.

Язык: Английский

Процитировано

19

Visible-Light-Antenna Ligand-Enabled Samarium-Catalyzed Reductive Transformations DOI
Takahito Kuribara,

Ayahito Kaneki,

Yu Matsuda

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(30), С. 20904 - 20912

Опубликована: Июль 20, 2024

Although divalent Sm reagents are some of the most important single-electron transfer for reductive transformations, their catalytic applications challenging. In this study, a bidentate phosphine oxide ligand substituted with 9,10-diphenylanthracene as visible-light antenna was designed Sm-catalyzed reduction reactions under mild reaction conditions. Pinacol coupling aryl ketones and aldehydes developed 1 mol % catalyst organic amine (DIPEA) sacrificial reductant. Mechanistic studies suggest that visible-light-antenna coordinates to Sm(III) reduces Sm(II) irradiation. The system is also applicable cross-pinacol other including aza-pinacol coupling, flavone dimerization, C-O bond cleavage, C-C ring-opening cyclopropane, ketyl-olefin cross-coupling ketyl radical α-amino radical.

Язык: Английский

Процитировано

9

Tunable C–H functionalization and dearomatization enabled by an organic photocatalyst DOI Creative Commons

Bohang An,

Hao Cui, Chao Zheng

и другие.

Chemical Science, Год журнала: 2024, Номер 15(11), С. 4114 - 4120

Опубликована: Янв. 1, 2024

Starting from the same substrates, tunable C–H functionalization and dearomatization have been achieved under catalysis of a new organic photocatalyst – isoazatruxene ITN-2.

Язык: Английский

Процитировано

5

A metalloenzyme platform for catalytic asymmetric radical dearomatization DOI
Wen‐Zhen Fu, Yue Fu, Yunlong Zhao

и другие.

Nature Chemistry, Год журнала: 2024, Номер 16(12), С. 1999 - 2008

Опубликована: Авг. 28, 2024

Язык: Английский

Процитировано

5

A blueprint for catalysis DOI
Ciro Romano, Jack I. Mansell, David J. Procter

и другие.

Nature Chemistry, Год журнала: 2024, Номер 16(3), С. 478 - 478

Опубликована: Март 1, 2024

Язык: Английский

Процитировано

3

Enantioselective Relay Coupling of Perfluoroalkyl and Vinylogous Ketyl Radicals DOI Creative Commons
Yuxin Zhao, Yichi Zhang, Yong Huang

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(35)

Опубликована: Июнь 12, 2024

Abstract β‐Chiral carboxylic acids and their derivatives are highly valuable structural motifs in the fields of asymmetric synthesis medicinal chemistry. However, introduction a sterically demanding sidechain to β‐carbon, such as an all‐carbon quaternary center, remains significant challenge classical polar processes. Recently, N ‐heterocyclic carbene (NHC) mediated coupling reactions involving persistent ketyl radicals have emerged promising strategy assemble crowded carbon‐carbon bonds. Nevertheless, achieving enantioselectivity these challenging. In this work, we report our recent progress controlling for relay perfluoroalkyl vinylogous radicals. We developed chiral bifunctional NHC‐squaramide catalyst that achieves high facial selectivity critical bond‐forming event congested tertiary carbon radical radical. Chiral carboxylates bearing center at β‐position can be prepared good yield excellent enantiomeric excess. Results from density functional theory (DFT) calculations nuclear Overhauser effect (NOE) experiments indicate , N’ ‐diaryl squaramide motif adopts unusual syn ‐ conformation, enabling hydrogen bonding interactions with enolate oxygen, thereby rigidifying overall conformation transition state.

Язык: Английский

Процитировано

3

(1S,1′S)-2,2′-(Benzylazanediyl)bis(1-((3aR,4R,6aR)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-yl)ethan-1-ol) DOI Creative Commons

Mohammed Kadraoui,

Stéphane Guillarme, Christine Saluzzo

и другие.

Molbank, Год журнала: 2025, Номер 2025(1), С. M1962 - M1962

Опубликована: Фев. 5, 2025

(1S,1′S)-2,2′-(Benzylazanediyl)bis(1-((3aR,4R,6aR)-2,2-dimethyltetrahydrofuro [3,4 d][1,3]dioxol-4-yl)ethan-1-ol), presenting a tertiary β-aminodiol moiety, was synthesized in 72% yield one-step reaction from an aminolysis of isosorbide-derived oxirane with benzylamine. This fully characterized by 1H and 13C NMR HRMS analyses.

Язык: Английский

Процитировано

0

Decoding the mechanism of P450-catalyzed aromatic hydroxylation: Uncovering the arene oxide pathway and insights into the regioselectivity DOI
Qun Huang, Xuan Zhang,

Guangwu Sun

и другие.

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Год журнала: 2025, Номер 70, С. 420 - 430

Опубликована: Март 1, 2025

Язык: Английский

Процитировано

0

Divergent and Enantioselective Synthesis of Three Types of Chiral Polycyclic N-Heterocycles via Copper-Catalyzed Dearomative Cyclization DOI Creative Commons
Wenfeng Luo, Li‐Gao Liu,

Yanxin Zheng

и другие.

ACS Central Science, Год журнала: 2025, Номер 11(5), С. 805 - 815

Опубликована: Май 2, 2025

Significant advancements have been made in the catalytic asymmetric dearomatization of indoles for constructing valuable chiral polycyclic N-heterocycles. However, dearomative cyclopropanation continues to pose a formidable challenge. Furthermore, diverse transformations indoline-fused cyclopropanes via strain release remain largely unexplored, potentially unveiling new chemistry. Here, we disclose Cu-catalyzed indole-diynes and subsequent [3 + 2] cycloaddition with oxygen, facilitating divergent atom-economical synthesis enantioenriched cyclopropane- 1,2-dioxolane-fused indolines moderate excellent yields generally outstanding diastereo- enantioselectivities broad substrate scope. Importantly, this protocol not only represents first utilizing alkynes as carbene precursors but also constitutes construction 1,2-dioxolanes high stereoselectivity. Interestingly, Brønsted acid-promoted ring-opening rearrangement cyclopropane-fused display distinctive chemoselectivity afford cyclohepta-[b]-indoles good efficiency enantiocontrol. In addition, both potential reaction pathways origins control within tandem sequence are robustly supported by experiments theoretical calculations.

Язык: Английский

Процитировано

0

Copper‐Catalyzed Oxygenative Skeletal Rearrangement of Tetrahydro‐β‐carbolines Using H2O and O2 as Oxygen Sources DOI

Yusheng Peng,

Wei Wang, Jun Shi

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(51)

Опубликована: Ноя. 11, 2023

Herein, we report an unprecedented skeletal rearrangement reaction of tetrahydro-β-carbolines enabled by copper-catalyzed single-electron oxidative oxygenation, in which H2 O and O2 act as oxygen sources to generate a unique 2-hydroxyl-3-peroxide indoline intermediate. The synthetic reactivity species was demonstrated multi-step bond cleavage formation cascade. Using readily available copper catalyst under open-air conditions, highly important yet synthetically difficult spiro[pyrrolidone-(3,1-benzoxazine)] products were obtained single operation. utility this methodology is the efficient synthesis natural donaxanine chimonamidine, well 3-hydroxyl-pyrroloindoline scaffold, just one or two steps.

Язык: Английский

Процитировано

6