Organic Letters, Год журнала: 2024, Номер unknown
Опубликована: Дек. 23, 2024
Herein we present photoinduced cobaloxime-catalyzed selective remote desaturation of aliphatic alcohols. This transformation, which proceeds efficiently at room temperature, facilitates the synthesis valuable cyclic and acyclic allylic homoallylic alcohols from readily available saturated Remarkably, this method obviates need for external oxidants, noble metal catalysts, phosphine ligands.
Язык: Английский
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(20)
Опубликована: Фев. 24, 2023
Glycosyl anomeric radical addition reactions have been well-explored and proved efficient for the C-alkyl glycosides synthesis, but multicomponent Domino transformations rapid controllable construction of structurally diversified in a single step are still rare. In contrast, we, herein, report ruthenium(II)-catalyzed meta-C-H ethyl glycosylation, enabling challenging meta-C-alkyl glycosides. Our ruthenium(II) catalysis was reflected by mild reaction condition, exclusive meta-site selectivity high levels selectivity. addition, glycosylation allowed synthesis versatile 1,2-trans-C-alkyl with commercially available vinyl arenes, acrylates easily accessible glycosyl bromides.
Язык: Английский
Процитировано
27
Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(32)
Опубликована: Май 9, 2022
Distal C(sp2 )-H and C(sp3 functionalizations have recently emerged as step-economical tools for molecular synthesis. However, while the )-C(sp3 ) construction is of fundamental importance, its formation through double remote )-H/C(sp3 activation has proven elusive. By merging ruthenium-catalyzed meta-C(sp2 functionalization with an aliphatic hydrogen atom transfer (HAT) process, we, herein, describe catalyzed twofold via photo-induced ruthenium-mediated radical relay. Thus, arene bonds alkane were activated by a single catalyst in operation. This process was accomplished at room temperature visible light-notably without exogenous photocatalysts. Experimental computational theory studies uncovered manifold comprising ortho-C-H activation, single-electron-transfer (SET), 1,n-HAT (n=5-7) σ-activation means ruthenium(II) catalyst.
Язык: Английский
Процитировано
36
Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(42)
Опубликована: Июль 25, 2022
Abstract The prevalence of C ‐aryl glycosides in biologically active natural products and approved drugs has long motivated the development efficient strategies for their selective synthesis. Cross‐couplings have been frequently used, but largely relied on palladium catalyst with prefunctionalized substrates, while ruthenium‐catalyzed glycoside preparation thus far proven elusive. Herein, we disclose a versatile ruthenium(II)‐catalyzed meta ‐C−H glycosylation to access ‐ from readily available glycosyl halide donors. robustness ruthenium catalysis was reflected by mild reaction conditions, outstanding levels anomeric selectivity exclusive ‐site‐selectivity.
Язык: Английский
Процитировано
29
Organic Letters, Год журнала: 2024, Номер 26(2), С. 427 - 432
Опубликована: Янв. 8, 2024
A mild approach to the visible-light-mediated bimetal-catalyzed meta-alkylation of arenes has been accomplished. The regioselective is realized by a bimetallic ruthenium–palladium system. Ruthenium acts as catalyst for directing effect and photosensitizer, while cocatalyst palladium behaves generation fluoroalkyl radicals. This reaction not only suitable two-component meta-fluoroalkylation but can also be extended three-component reactions achieve bifunctionalization olefins.
Язык: Английский
Процитировано
8
Nature Synthesis, Год журнала: 2025, Номер unknown
Опубликована: Фев. 17, 2025
Язык: Английский
Процитировано
1
Organic Letters, Год журнала: 2022, Номер 24(30), С. 5584 - 5589
Опубликована: Июль 27, 2022
We report a visible-light-induced iron-catalyzed α-alkylation of ketones. The photocatalytic system is based on the single diaminocyclopentadienone iron tricarbonyl complex. Two catalytic intermediates this complex are able to harvest light, allowing synthesis substituted aromatic and aliphatic ketones at room temperature using borrowing hydrogen strategy in presence various primary alcohols as alkylating reagents. Preliminary mechanistic studies unveil role light for both dehydrogenation reduction step.
Язык: Английский
Процитировано
28
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(22)
Опубликована: Фев. 27, 2023
Ruthenium-catalyzed σ-bond activation-assisted meta-C-H functionalization has emerged as a useful tool to forge distal C-C bonds. However, given the limited number of mechanistic studies, clear understanding origin site-selectivity and complete reaction pattern is not available. Here, we present systematic computational studies on ruthenium-catalyzed C-H with primary, secondary, tertiary alkyl bromides aryl bromides. The scission formation were carefully examined. Monocyclometalated ruthenium(II) complexes identified active species, which then underwent inner-sphere single electron transfer (ISET) activate organic results from competition between close-shell reductive elimination open-shell radical coupling. Based this understanding, multilinear regression model was built predict site-selectivity, further validated by experiments.
Язык: Английский
Процитировано
15
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(26)
Опубликована: Апрель 22, 2023
Twofold distal C-H functionalization was accomplished by difunctionalization of nonactivated alkenes to provide rapid access multifunctionalized molecules. The multicomponent ruthenium-catalyzed remote 1,n-difunctionalization (n=6,7) with fluoroalkyl halides and heteroarenes in a modular manner is reported. meta-C(sp2 )-H/C-6(sp3 )-H featured mild conditions, unique selectivity, broad substrate scope domino process for twofold C(sp2 )-H/C(sp3 activation the sequential formation three different carbon-centered radicals. A plausible mechanism proposed based on detailed experimental computational studies.
Язык: Английский
Процитировано
14
ACS Catalysis, Год журнала: 2023, Номер 13(11), С. 7310 - 7321
Опубликована: Май 15, 2023
Anilines are important moieties in organic chemistry, pharmaceuticals, and materials science. Although para-selective functionalization of anilides tertiary anilines is well established, unprotected have posed a challenge. Herein, we report visible-light-mediated Ru(II)-catalyzed para-alkylation anilines. The distinct Ru(II)–aniline complex enabled the reaction to proceed with extremely high efficiency (2 h) under mild conditions. good functional group tolerance allowed late-stage even aggregation-induced emission luminogen labeling natural products drugs. A mechanistic investigation suggests that crucial for both triggering controlling para-selectivity.
Язык: Английский
Процитировано
14
Organic Letters, Год журнала: 2024, Номер 26(15), С. 3213 - 3217
Опубликована: Апрель 4, 2024
With in-depth research on 1,2-difunctionalization, remote difunctionalization has garnered widespread attention for achieving multifunctionality. Herein, we report a strategy under mild conditions. This exhibited good substrate suitability and functional group tolerance. In addition, the significance of this method is further evidenced by its successful application in scaling up conducting additional transformations target compounds. Mechanistic studies showed that radical might be involved process.
Язык: Английский
Процитировано
6