Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(26)
Published: April 18, 2024
C(sp
Language: Английский
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)
Published: Feb. 3, 2024
Abstract Pyridine motifs are widespread pharmacophores in many drugs. Installing various substituents through pyridine C−H bond functionalization is significant for new drug design and discovery. Developments of late‐stage reactions enrich the strategies selective pyridines. However, carboxylation pyridines a long‐standing challenge, especially selectively with CO 2 on motifs. Herein, we describe practical method C4−H via one‐pot phosphination copper‐catalyzed resulted phosphonium salts . The reaction conducted under mild conditions compatible multiple active groups several drugs, providing diverse valuable isonicotinic acid compounds, demonstrating application potential this strategy.
Language: Английский
Citations
11
Organic Letters, Journal Year: 2022, Volume and Issue: 24(44), P. 8218 - 8222
Published: Nov. 2, 2022
The first example of the 3-position-selective C(sp2)-H trifluoromethylation pyridine rings was established. 3-Position-selective achieved by nucleophilic activation and quinoline derivatives through hydrosilylation successive electrophilic enamine intermediate. This reaction applicable to perfluoroalkylation at 3 position late-stage a bioactive molecule. Mechanistic studies indicated that proceeds via formation N-silyl trifluoromethylated intermediates.
Language: Английский
Citations
33
Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(6)
Published: Dec. 15, 2022
Methods for C-H cyanation of pyridines are rare. Here, we report a method C3-selective by tandem process with the reaction an in situ generated dihydropyridine cyano electrophile as key step. The is suitable late-stage functionalization pyridine drugs. low reduction potential and effective transfer nitrile group were found to be essential success this method. We studied mechanism detail means control experiments theoretical calculations that combination electronic steric factors determined regioselectivity reactions involving C2-substituted pyridines.
Language: Английский
Citations
30
Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 145(1), P. 25 - 31
Published: Dec. 22, 2022
Heterocycles are the backbone of modern medical chemistry and drug development. The derivatization "an olefin" inside aromatic rings represents an ideal approach to access functionalized saturated heterocycles from abundant building blocks. Here, we report operationally simple, efficient, practical method selectively hydrosilylated reduced N-heterocycles bicyclic aromatics via a key diradical intermediate. This is expected facilitate complex heterocycle functionalizations that enable novel medicinally relevant scaffolds.
Language: Английский
Citations
29
Chem, Journal Year: 2023, Volume and Issue: 10(2), P. 628 - 643
Published: Nov. 21, 2023
Language: Английский
Citations
23
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: Aug. 28, 2024
Considering the indispensable significance and utilities of meta-substituted pyridines in medicinal, chemical as well materials science, a direct meta-selective C-H functionalization is paramount importance, but such reactions remain limited highly challenging. In general, established methods for meta rely on utilization tailored electrophilic reagents to realize intrinsic polarity match. Herein, we report complementary electrochemical methodology; diverse nucleophilic sulfinates allow meta-sulfonylation through redox-neutral dearomatization-rearomatization strategy by tandem dearomative cycloaddition/hydrogen-evolution electrooxidative sulfonation resulting oxazino-pyridines/acid-promoted rearomatization sequence. Besides, several salient features, including exclusive regiocontrol, remarkable substrate/functional group compatibility, scale-up potential, facile late-stage modification, have been demonstrated, which further contributes practicality adaptability this approach.
Language: Английский
Citations
9
iScience, Journal Year: 2024, Volume and Issue: 27(2), P. 108781 - 108781
Published: Jan. 6, 2024
Tandem reactions involve multi-step processes conducted in one pot, offering a cost-effective, environmentally friendly, and efficient approach to chemical transformations with high atom economy. The catalytic systems employed tandem are crucial for achieving desirable activity, selectivity, stability. Researchers worldwide have extensively explored driven by various energy fields, such as electrocatalysis, thermocatalysis, photocatalysis, aiming facilitate multiple bond transformations. Continuous advancements been made reaction conditions, catalyst design, preparation methods. This review provides comprehensive overview of recent progress reactions, specifically focusing on electro-, thermo-, categorizes them into catalysts, reactors, fields based their applications. Furthermore, the highlights significance rational design nanomaterial catalysts integration sources, emphasizing potential enhance performance, development combined catalysis.
Language: Английский
Citations
7
Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(27)
Published: May 13, 2022
Herein we disclose a mild protocol for the reductive functionalisation of quinolinium and isoquinolinium salts. The reaction proceeds under transition-metal-free conditions as well rhodium catalysis with very low catalyst loadings (0.01 mol %) uses inexpensive formic acid terminal reductant. A wide range electrophiles, including enones, imides, unsaturated esters sulfones, β-nitro styrenes aldehydes are intercepted by in situ formed enamine species forming large variety substituted tetrahydro(iso)quinolines. Electrophiles incorporated at C-3 C-4 position quinolines isoquinolines respectively, providing access to substitution patterns which not favoured electrophilic or nucleophilic aromatic substitution. Finally, this reactivity was exploited facilitate three types annulation reactions, giving rise complex polycyclic products formal [3+3] [4+2] cycloaddition.
Language: Английский
Citations
25
Organic Letters, Journal Year: 2023, Volume and Issue: 25(1), P. 87 - 92
Published: Jan. 3, 2023
Regioselective hydroboration of pyridines to 1,2-dihydropyridines remains a significant challenge for the synthesis valuable nitrogenous bioactive molecules. Herein, we report base free ligand-controlled cobalt-catalyzed 1,2-hydroboration and quinolines with very low catalyst loading under neat reaction conditions. The choice sterically demanding N-heterocyclic ligands led 1,2-regioselectivity scope was demonstrated by N-heterocycles having variety functional groups. preliminary mechanistic studies corroborate that two followed distinct catalytic cycle Co(I) as an active species.
Language: Английский
Citations
16
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(8)
Published: Nov. 21, 2023
Abstract An arylation protocol for pyridines is described, via the ring‐opened Zincke intermediate. Treatment of with triflic anhydride and a secondary amine produces an azahexatriene species, which undergoes regioselective Pd‐catalyzed at putative C4 position. Recyclization then provides pyridine products. Alternatively, metal‐free diaryliodonium salt selective meta ‐position, affording regiodivergent approach to biaryls from common
Language: Английский
Citations
14