Trends in Chemistry, Journal Year: 2022, Volume and Issue: 4(12), P. 1062 - 1064
Published: Sept. 20, 2022
Language: Английский
Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(12), P. 4099 - 4120
Published: Jan. 1, 2023
sp 3 C–H functionalizations under the combination of photocatalytic HAT and transition metal catalysis.
Language: Английский
Citations
98
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown
Published: Oct. 3, 2024
The polarity of a radical intermediate profoundly impacts its reactivity and selectivity. To quantify this influence predict effects, the electrophilicity/nucleophilicity >500 radicals has been calculated. This database open-shell species entails frequently encountered synthetic intermediates, including centered at sp
Language: Английский
Citations
45
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(22), P. 12224 - 12232
Published: May 24, 2023
Photoinduced enhancement of hydricity palladium hydride species enables unprecedented addition-like (“hydridic”) hydropalladation electron-deficient alkenes, which allows for chemoselective head-to-tail cross-hydroalkenylation and electron-rich alkenes. This mild general protocol works with a wide range densely functionalized complex Notably, this approach also highly challenging cross-dimerization electronically diverse vinyl arenes heteroarenes.
Language: Английский
Citations
31
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(7), P. 4985 - 4992
Published: Feb. 6, 2024
Unsaturated amides represent common functional groups found in natural products and bioactive molecules serve as versatile synthetic building blocks. Here, we report an iron(II)/cobalt(II) dual catalytic system for the syntheses of distally unsaturated amide derivatives. The transformation proceeds through iron nitrenoid-mediated 1,5-hydrogen atom transfer (1,5-HAT) mechanism. Subsequently, radical intermediate undergoes hydrogen abstraction from vicinal methylene by a cobaloxime catalyst, efficiently yielding β,γ- or γ,δ-unsaturated derivatives under mild conditions. efficiency Co-mediated HAT can be tuned varying different auxiliaries, highlighting generality this protocol. Remarkably, desaturation protocol is also amenable to practical scalability, enabling synthesis carbamates ureas, which readily converted into various valuable molecules.
Language: Английский
Citations
7
Nature, Journal Year: 2024, Volume and Issue: 634(8033), P. 352 - 358
Published: Aug. 29, 2024
Language: Английский
Citations
7
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 3882 - 3890
Published: Feb. 13, 2023
Site-selective functionalization of unactivated C(sp3)–H centers is challenging because the ubiquity and strength alkyl C–H bonds. Herein, we disclose a position-selective C(sp3)–C(sp2) cross-coupling reaction. This process engages bonds aryl bromides, utilizing catalytic quantities photoredox-capable molecule nickel precatalyst. Using this technology, selective arises owing to 1,6-hydrogen atom transfer (HAT) that guided by pendant alcohol-anchored sulfamate ester. These transformations proceed directly from N–H bonds, in contrast previous directed, radical-mediated, arylation processes, which have relied on prior oxidation reactive nitrogen center reactions with nucleophilic arenes. Moreover, these conditions promote at secondary good yields excellent selectivity.
Language: Английский
Citations
14
The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(15), P. 11240 - 11252
Published: July 25, 2023
We present protocols for the oxidation of alcohols and aldehydes oxidative cyclization diols which use a combination Selectfluor NaBr. For most substrates, optimal solvent system is 1:1 mixture CH3CN/H2O, but, in select cases, biphasic mixtures EtOAc/H2O or CH2Cl2/H2O are superior. This procedure operationally simple, uses inexpensive readily available reagents, tolerates variety functional groups. Mechanistic studies suggest that active oxidant hypobromous acid, generated by almost instantaneous Br– an aqueous milieu.
Language: Английский
Citations
11
ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2402 - 2408
Published: Jan. 31, 2024
Unstrained carbon–carbon bonds are among the most prevalent and inert chemical bonds. Thus, developing synthetic transformations directly from unstrained under mild conditions is ideal yet challenging due to inertness steric hindrance. Here, a visible-light copper-catalyzed azidation etherification of remote C–C bond amines via 1,4-aryl migration have been reported. This redox-neutral protocol shows exquisite site-selectivity, broad scope, good functional group tolerance, transforming C–N C–O at room temperature. Facile derivatizations benzyl azide products into free amines, triazoles, phosphamides highlight potential utility this method for target molecule synthesis medicinal chemistry.
Language: Английский
Citations
4
ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 8005 - 8012
Published: May 9, 2024
We report intra- and intermolecular γ-amino C(sp3)–H functionalization of aliphatic amines using a vinylsulfone-based HAT (hydrogen atom transfer) auxiliary triple catalysis, which is composed photoredox, cobalt, Brønsted acid catalysts under visible light irradiation. The process accomplishes four elementary steps: (i) electrophilic carbon-centered radical formation on the via MHAT (metal hydride hydrogen reaction, (ii) generation through 1,6-HAT (iii) single-electron oxidation to carbocation equivalents, (iv) nucleophilic substitution with internal or external nucleophiles. As result, this afforded γ-amino-functionalized products, such as azetidines, 1,3-diamine, 1,3-aminoalcohol derivatives.
Language: Английский
Citations
4
Chem, Journal Year: 2024, Volume and Issue: 10(10), P. 3088 - 3099
Published: June 19, 2024
Language: Английский
Citations
4