The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown
Published: Sept. 23, 2024
Density functional theory was utilized to investigate the mechanism of Ru(II)-catalyzed aromatic C-H activation and addition aldehydes. The proposed catalytic cycle consists bond activation, aldehyde carbonyl insertion for C-C coupling, lactonization formation final product, product separation, catalyst recovery. Our calculations suggest that Ru(OAc)
Language: Английский
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(26)
Published: April 15, 2024
In contrast to the kinetically favored outward isomerization-hydrocarbonylation of alkenes, disfavored inward alkenes remains an important challenge. Herein, we have developed a novel and effective palladium-catalyzed isomerization-hydroaminocarbonylation unactivated aniline hydrochlorides for formation synthetically valuable α-aryl carboxylic amides in high yields site-selectivities. The efficiency reaction is attributed relay catalysis strategy, which Markovnikov-favored [PdH]-P
Language: Английский
Citations
11
ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 7243 - 7255
Published: April 24, 2024
The atroposelective direct C–H alkylation of heterobiaryls with simple alkenes represents a challenging and underexplored frontier. Herein we report an iridium(I)-catalyzed regiodivergent enantioselective 1-arylisoquinolines or 2-arylpyridines alkenes. By utilizing cationic iridium catalyst different types chiral bidentate phosphine ligands, both linear- branched-selective alkylations were achieved high regioselectivities enantioselectivities. With this atom-economic ligand-enabled protocol, series axially nitrogen-containing synthesized good efficiency enantioselectivity. For the linear-selective involving styrene moiety, computational investigations illuminated that regioselectivity is established during migratory insertion step into Ir–C bond. Both experimental density functional theory (DFT) studies concerning substituent effects moiety also conducted. These results suggest primacy role resonance effect relative to field-inductive in determining transformation.
Language: Английский
Citations
9
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: unknown
Published: Oct. 31, 2023
Hydroamination facilitated by metal hydride catalysis is an appealing synthetic approach to access valuable nitrogen-containing compounds from readily available unsaturated hydrocarbons. While high regioselectivity can be achieved usually for substrates bearing polar chelation groups, the reaction involving simple alkenes frequently provides nonselective outcomes. Herein, we report iridium-catalyzed highly regioselective terminal C(sp3)-H amidation of internal utilizing dioxazolones as amino source via olefin chain walking. Most notably, this mechanistic motif double bond migration position operates not only with dialkyl-substituted including styrenes but also heteroatom-substituted olefins such enol ethers, vinyl silanes, and borons, thus representing first example methyl latter type through a nondissociative walking process.
Language: Английский
Citations
12
Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14865 - 14871
Published: Jan. 1, 2024
A novel photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated alkenes with aryl bromides by using proton as a hydrogen source has been developed for the first time.
Language: Английский
Citations
3
Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6625 - 6630
Published: Aug. 1, 2024
By employing elemental selenium as the source, we have realized amidine-directed Rh(III)-catalyzed cascade C–H selenylation/[5 + 1] annulation for direct construction of structurally novel selenadiazine, benzoselenadiazine, and benzoselenazol-3-amine frameworks with specific site selectivity good functional group tolerance. Besides, obtained products can serve fundamental platforms subsequent chemical transformations, thus, feasible SeNEx reaction, SeNEx/Michael addition, simple conversion selenadiazine product into diverse other organoselenium molecules were demonstrated accordingly. Taken together, developed methodology efficiently expands space species.
Language: Английский
Citations
2
Organic Letters, Journal Year: 2023, Volume and Issue: 25(48), P. 8727 - 8732
Published: Nov. 29, 2023
The 1,3-rearrangement of allylic derivatives has rarely been reported, except for alcohols. Herein, we describe an iridium-catalyzed readily available ethers to access the difficultly prepared with a large steric hindrance. developed method shows broad substrate scope and could be used in late-stage modification several natural products. In addition, possible reaction pathway is also provided on basis control experiments.
Language: Английский
Citations
2
Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(26)
Published: April 15, 2024
Abstract In contrast to the kinetically favored outward isomerization‐hydrocarbonylation of alkenes, disfavored inward alkenes remains an important challenge. Herein, we have developed a novel and effective palladium‐catalyzed isomerization‐hydroaminocarbonylation unactivated aniline hydrochlorides for formation synthetically valuable α‐aryl carboxylic amides in high yields site‐selectivities. The efficiency reaction is attributed relay catalysis strategy, which Markovnikov‐favored [PdH]‐P t Bu 3 catalyst responsible isomerization, while [PdH]‐Ruphos hydroaminocarbonylation resulting conjugated aryl alkenes. exhibits highly functional group tolerance provides new method formal carbonylation remote C(sp )−H bond.
Language: Английский
Citations
0
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)
Published: June 5, 2024
Pyrroles and indoles bearing N-allenyl tethers participate in a variety of iridium-catalyzed cycloisomerization processes initiated by C-H activation step, to deliver diversity synthetically relevant azaheterocyclic products. By appropriate selection the ancillary ligand substitution pattern allene, reactions can diverge from simple intramolecular hydrocarbonations tandem involving intriguing mechanistic issues. Accordingly, wide range heterocyclic structures ranging dihydro-indolizines pyridoindoles tetrahydroindolizines, as well cyclopropane-fused tetrahydroindolizines be obtained. Moreover, using chiral ligands, these cascade carried out an enantioselective manner. DFT studies provide insights into underlying mechanisms justify observed chemo- regio- stereoselectivities.
Language: Английский
Citations
0
Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(36)
Published: June 5, 2024
Abstract Pyrroles and indoles bearing N ‐allenyl tethers participate in a variety of iridium‐catalyzed cycloisomerization processes initiated by C−H activation step, to deliver diversity synthetically relevant azaheterocyclic products. By appropriate selection the ancillary ligand substitution pattern allene, reactions can diverge from simple intramolecular hydrocarbonations tandem involving intriguing mechanistic issues. Accordingly, wide range heterocyclic structures ranging dihydro‐indolizines pyridoindoles tetrahydroindolizines, as well cyclopropane‐fused tetrahydroindolizines be obtained. Moreover, using chiral ligands, these cascade carried out an enantioselective manner. DFT studies provide insights into underlying mechanisms justify observed chemo‐ regio‐ stereoselectivities.
Language: Английский
Citations
0
Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(17), P. 3610 - 3615
Published: July 2, 2024
Abstract A mechanism‐navigated enantioselective alkylation of an indole C2 C−H bond with internal alkene was developed. Under the unconventional ligand‐to‐metal catalyst ratio, a moderate enantiomeric ratio (er), ranging from 70:30 to 88:12, achieved our original ligand. We propose that chain‐walking and formation are mechanistically independent suggest hydridoiridium generated source does not play role in process.
Language: Английский
Citations
0