Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(40), P. 8102 - 8108
Published: Jan. 1, 2024
A practical electrochemical sulfonylation-triggered Truce–Smiles rearrangement of N -allylbenzamides yielded sulfone- and sulfonic acid-containing β-arylethylamines under mild oxidant-free reaction conditions.
Language: Английский
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(44), P. 24175 - 24183
Published: Oct. 27, 2023
The arylation of 2-alkyl aziridines by nucleophilic ring-opening or transition-metal-catalyzed cross-coupling enables facile access to biologically relevant β-phenethylamine derivatives. However, both approaches largely favor C–C bond formation at the less-substituted carbon aziridine, thus enabling only linear products. Consequently, despite attractive disconnection that it poses, synthesis branched arylated products from has remained inaccessible. Herein, we address this long-standing challenge and report first branched-selective with aryl iodides. This unique selectivity is enabled a Ti/Ni dual-catalytic system. We demonstrate robustness method twofold approach: an additive screening campaign probe functional group tolerance feature-driven substrate scope study effect local steric electronic profile each coupling partner on reactivity. Furthermore, diversity generation predictive reactivity models guided mechanistic understanding. Mechanistic studies demonstrated arises TiIII-induced radical aziridine.
Language: Английский
Citations
27
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 10, 2025
The cycloaddition of aziridines with unsaturated compounds is a valuable method for synthesizing nitrogen heterocycles. However, this process predominantly substrate-controlled, posing significant challenges in regulating the regioselectivity C–N bond cleavage. In study, we report nickel-catalyzed dynamic kinetic activation strategy that enables catalyst-controlled aziridines. Various types aziridines, including 2-phenyl, 2-carbonyl, 2-alkyl, and disubstituted consistently cleave their more sterically hindered bonds to generate 1,3-radical anion intermediates. These intermediates participate highly regioselective 1,4-Heck/allylic substitution cascade aromatic branched 1,3-dienes, resulting radical-polar crossover (4 + 3) produces seven-membered azepine products. This approach not only complements traditional dipolar cycloaddition, which typically act as zwitterionic 1,3-dipoles, but also introduces an unusual mode 1,3-dienes. Experimental investigations density functional theory (DFT) calculations provide insight into reaction mechanism.
Language: Английский
Citations
1
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: March 10, 2025
The transition-metal-catalyzed ring-opening functionalization of aziridines presents a promising approach for synthesizing structurally complex amines. However, the rearranged poses significant challenges. Herein, we report first alkenylation with aryl alkenes via Ni-Brønsted acid co-catalysis, leading to rapid synthesis diverse array allylamines yields reaching up 91%. Mechanistic studies suggest that reaction occurs through rearrangement aziridine generate an imine intermediate. This intermediate is subsequently captured by alkene under nickel catalysis, ultimately formation allylamines.
Language: Английский
Citations
1
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25426 - 25432
Published: Sept. 4, 2024
Herein, we report the first example of a highly enantioselective alkylative aziridine ring opening. Under catalysis chiral nickel/pyridine-imidazoline complex, asymmetric C(sp
Language: Английский
Citations
6
Acta Chimica Sinica, Journal Year: 2024, Volume and Issue: 82(2), P. 190 - 190
Published: Jan. 1, 2024
Language: Английский
Citations
5
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)
Published: Aug. 21, 2023
Abstract β‐(Hetero)arylethylamines appear in a myriad of pharmaceuticals due to their broad spectrum biological properties, making them prime candidates for drug discovery. Conventional methods preparation often require engineered substrates that limit the flexibility synthetic routes and diversity compounds can be accessed. Consequently, provide rapid versatile access those scaffolds remain limited. To overcome these challenges, chemists have designed innovative modular strategies β‐(hetero)arylethylamine motif, paving way more extensive use future pharmaceuticals. This review outlines recent progresses synthesis (hetero)arylethylamines emphasizes how innovations enabled new levels molecular complexity, selectivity, practicality.
Language: Английский
Citations
13
The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(4), P. 2247 - 2263
Published: Feb. 7, 2024
A simple and atom economic protocol for the construction of C–X/C–C bonds via catalytic aminium radical-cation salt (Magic Blue)-initiated SN2-type nucleophilic ring-opening transformations racemic nonracemic aziridines with different hetero carbon nucleophiles to afford various amino ethers, thioethers, amines in up 99% yield, perfect enantiospecificity some substrates but reduced ee others (for aziridines), is developed. This salt-initiated, strategy, along cyclization protocols, employed synthesize biologically significant compounds.
Language: Английский
Citations
4
Organic Letters, Journal Year: 2024, Volume and Issue: unknown
Published: Sept. 12, 2024
An efficient approach for the remote C-H alkylation of arenes, employing a variety N-directing groups is described. This method facilitates straightforward synthesis valuable phenylethylamine derivatives by exclusively cleaving benzylic C-N bond in aziridines. Furthermore, these products can easily remove protecting groups, resulting meta-substituted compounds, such as amines and ketones, which hold significance synthetic chemistry.
Language: Английский
Citations
4
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(47), P. 32249 - 32254
Published: Nov. 15, 2024
Sacrificial anodes composed of inexpensive metals such as Zn, Fe, and Mg are widely used to support electrochemical nickel-catalyzed cross-electrophile coupling (XEC) reactions, in addition other reductive transformations. Such appealing because they provide a stable counter-electrode potential typically avoid interference with the chemistry. The present study outlines development an Ni-catalyzed XEC reaction that streamlines access key pharmaceutical intermediate. Metal ions derived from sacrificial anode oxidation, however, directly contribute homocoupling proto-dehalogenation side products commonly formed chemical reactions. Use divided cell limits by anode-derived metal supports high product yield negligible formation, introducing strategy overcome one main limitations XEC.
Language: Английский
Citations
4
Organic Letters, Journal Year: 2025, Volume and Issue: 27(4), P. 989 - 994
Published: Jan. 21, 2025
Herein, we report an electricity-driven activation of aziridine via direct anodic oxidation to give N-heterocycles and 1,2-bifunctionalized products by excluding any oxidant/reductant or metal catalyst. Many structurally modified aziridines were employed in the presence different nitriles. A large variety nucleophiles screened furnish chemoselectively O-alkylated C-alkylated products. Late-stage derivatization with natural medicinally active compounds has also been done. Remarkably, our strategy was found be a greener, sustainable, atom-economical approach (E-factor = ca. 0.8). Azetidine compatible protocol generated six-membered N-heterocycles. The detailed mechanistic study highlighted that reaction is driven generation radical cation followed SN2 nucleophilic attack.
Language: Английский
Citations
0