Amorphous Fe0.8Mn0.2Ox-Catalyzed Four-Step Tandem Synthesis of Benzazoles from Alcohols and o-Substituted Anilines without Solvent DOI

Linkun Dong,

Jiaheng Qin,

Jing Chen

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(42), P. 15461 - 15471

Published: Oct. 7, 2024

Benzazoles, as crucial intermediates, can be synthesized via a superior four-step tandem catalytic process from benzyl alcohols and o-substituted anilines. However, the reported catalysis system needs complex catalysts, toxoneic solvents, additives; meanwhile, efficient synthesis of benzimidazoles, benzoxazoles, benzothiazoles using single catalyst represents substantial challenge in field synthetic chemistry. Herein, we constructed an amorphous Fe0.8Mn0.2Ox-300 by simple coprecipitation method. efficiently catalyze 2-arylbenzimidazole, 2-arylbenzoxazole, 2-arylbenzothiazole alcohol, o-phenylenediamine, 2-aminophenol, 2-aminothiophenol, respectively, O2 without solvent additives. Comprehensive characterization revealed that possesses more oxygen vacancies stronger capture capability, promoting oxidation alcohol 2-aryl-2,3-dihydro-1H-benzimidazole. Due to its high density acidic sites, effectively boosts condensation cyclization aldehydes amines while simultaneously inhibiting formation diamines, thereby enhancing overall selectivity. Our work presents alternative green approach for industrial benzazoles.

Language: Английский

Enantioselective synthesis of molecules with multiple stereogenic elements DOI Creative Commons
Arthur Gaucherand, Expédite Yen‐Pon,

Antoine Domain

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(22), P. 11165 - 11206

Published: Jan. 1, 2024

This review explores the fascinating world of molecules featuring multiple stereogenic elements, unraveling different strategies designed over years for their enantioselective synthesis.

Language: Английский

Citations

12
A Spectroscopic Criterion for Identifying the Degree of Ground-Level Near-Degeneracy Derived from Effective Hamiltonian Analyses of Three-Coordinate Iron Complexes DOI Creative Commons
Wang Chen,

Н. А. Кочетов,

Thomas Lohmiller

et al.

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 1016 - 1030

Published: Feb. 6, 2025

The fascinating magnetic and catalytic properties of coordinatively unsaturated 3d metal complexes are a manifestation their electronic structures, in particular nearly doubly or triply degenerate orbital ground levels. Here, we propose criterion to determine the degree degeneracy this class based on experimentally accessible anisotropy (parametrized by electron spin g- zero-field splitting (ZFS)-tensors). is derived from comprehensive spectroscopic theoretical study trigonal planar iron(0) complex, [(IMes)Fe(dvtms)] (IMes = 1,3-di(2′,4′,6′-trimethylphenyl)imidazol-2-ylidene, dvtms divinyltetramethyldisiloxane, 1). Accurate ZFS-values (D +33.54 cm–1, E/D 0.09) g-values (g∥ 1.96, g⊥ 2.45) triplet (S 1) level complex 1 were determined complementary THz-EPR spectroscopy SQUID magnetometry. In-depth effective Hamiltonian (EH) analyses coupled wave-function-based ab initio calculations show that features with three energetically close-lying states "two-above-one" energy pattern. observed results mixing two excited state spin–orbit coupling (SOC). EH investigations related allowed us generalize finding establish ZFS-tensors as markers for assigning two- three-fold near-degeneracy.

Language: Английский

Citations

0
Three-Coordinate Iron(0) Complex-Catalyzed Regioselective C–H Alkylation of Indole Derivatives DOI Creative Commons
Zijing Zhang,

Stéphane Golling,

Silvia Cattani

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

The synthesis of alkylated indoles, which are key intermediates for various drugs and bioactive molecules, is great importance. However, most reports on the functionalized indoles use toxic expensive 4d or 5d metal catalysts, limiting further application these methods. Herein, we disclose a versatile regioselective C–H alkylation indole derivatives using well-defined three-coordinate iron(0) complex. Neither Grignard reagents nor additional additives required, making reaction sustainable, environmentally friendly, compatible with broad variety functional groups to afford C2-alkylated in high yields. In addition, by variation aryl substituent alkene substrate trisubstituted silyl group, regioselectivity can be altered from Markovnikov anti-Markovnikov. Detailed mechanistic studies revealed catalytic mode reaction.

Language: Английский

Citations

0
Rhodium-Catalyzed Atroposelective C–H Alkylation of 1-Aryl Isoquinoline Derivatives with Cyclopropanols DOI
Wenwen Zhang, Quannan Wang, Chao Zheng

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4017 - 4024

Published: Feb. 20, 2025

Language: Английский

Citations

0
Ligand Influence on the Performance of Cesium Lead Bromide Perovskite Quantum Dots in Photocatalytic C(sp3)–H Bromination Reactions DOI Creative Commons
Willi M. Amberg, Henry Lindner, Yeşim Şahin

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 28, 2025

Lead halide perovskite quantum dots (LHP QDs) CsPbX3 generate immense interest as narrow-band emitters for displays, lasers, and light sources. All QD applications rely on suited engineering of surface capping ligands. The first generation LHP QDs employed oleic acid/oleyl amine have found only a limited use in photoredox catalysis. These catalysts been reported to be unstable decompose over the course reaction, thus reducing turnover numbers (TONs) limiting their synthetic ability. Herein, impact eight distinct ligands monodisperse CsPbBr3 is reported, affording thorough comprehension performance photocatalytic C–H brominations. efforts yielded operating at extremely low catalyst loadings (<100 ppb) with TONs 9,000,000 per QD. We emphasize that optimal catalytic requires increased accessibility without compromising structural colloidal integrity. Control experiments indicated well-known such Ir(ppy)3, Ru(bpy)3Cl2, or 4CzlPN are ineffective same reaction. Mechanistic studies reveal C–Br bond reduction CH2Br2 rate-limiting step likely facilitated through interaction surface. This work outlines holistic approach toward design practically useful photocatalysts out comprising structurally soft cores dynamically bound

Language: Английский

Citations

0
P(═O)R2-Directed Asymmetric Catalytic C–H Olefination Leading to C–N Axially Chiral Targets DOI

Shengzhou Jin,

Yu Wang, Jun Yan

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

A novel P(═O)R2-directed asymmetric catalytic olefination has been developed, enabling efficient access to carbon–nitrogen axially chiral products with excellent yields (up 92%) and enantioselectivity 99% enantiomeric excess). The synergistic coordination of phosphine oxide functionality l-pGlu-OH the Pd metal center, serving as an directing group ligand, was key success this C–H functionalization system. reaction demonstrated a broad substrate scope, yielding 33 distinct C–N axial products. absolute configuration unambiguously confirmed via X-ray diffraction analysis. Additionally, three representative applications were showcased, involving reduction oxidation produce phosphines related derivatives. plausible cycle mechanism proposed, supported by detailed experimental studies. Aggregates in system identified aggregation-induced polarization experiments.

Language: Английский

Citations

0
Pentafluorosulfanoxylation of Hypervalent Chlorines and Bromines for Access to Pentafluoro(biaryloxy)-λ6-sulfanes DOI

Jia‐Yi Shou,

Feng‐Ling Qing

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

The SF5O group has been less explored as a highly fluorinated substituent on an organic framework. In fact, only few SF5O-containing compounds have reported, and the preparation of relied hazardous reagents special apparatuses. Herein we describe safe efficient access to various pentafluoro(aryloxy)-λ6-sulfanes (ArOSF5) through reaction hypervalent λ3-chlor(brom)anes with [Et3MeN]+[OSF5]−. synthetic application potentials ArOSF5 moieties were demonstrated by inertness OSF5 in presence palladium catalysts, alkalis, nucleophiles.

Language: Английский

Citations

0
Acylsilanes as Weakly Coordinating Directing Groups for Metal-Catalyzed C–H Functionalization DOI
Rowan L. Pilkington, Daniel L. Priebbenow

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6881 - 6894

Published: April 14, 2025

Language: Английский

Citations

0
Rhodium(III)-Catalyzed Redox-Neutral [4 + 2] Annulation of 3,5-Diaryloxadiazoles with Alkynes: A Dual C–H Activation Strategy for Constructing C–N Atropisomers DOI
Siyuan Li, Yong Han, Zhen Yang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

A rhodium(III)-catalyzed dual-ring formation via cascade C-H activation/[4 + 2] annulation of 3,5-diaryoxadiazoles with alkynes was developed. This strategy has been demonstrated a variety 3,5-diaryloxadiazoles and alkynes, it successfully scaled up to gram-scale synthesis, highlighting its potential significance in the direct construction C-N atropisomers. Furthermore, cleavage N-O bond is essential for bicyclic structure absence an external oxidant. Mechanistic studies revealed that at 3-phenyl group oxadiazole likely rate-determining step this reaction.

Language: Английский

Citations

0
Amorphous Fe0.8Mn0.2Ox-Catalyzed Four-Step Tandem Synthesis of Benzazoles from Alcohols and o-Substituted Anilines without Solvent DOI

Linkun Dong,

Jiaheng Qin,

Jing Chen

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(42), P. 15461 - 15471

Published: Oct. 7, 2024

Benzazoles, as crucial intermediates, can be synthesized via a superior four-step tandem catalytic process from benzyl alcohols and o-substituted anilines. However, the reported catalysis system needs complex catalysts, toxoneic solvents, additives; meanwhile, efficient synthesis of benzimidazoles, benzoxazoles, benzothiazoles using single catalyst represents substantial challenge in field synthetic chemistry. Herein, we constructed an amorphous Fe0.8Mn0.2Ox-300 by simple coprecipitation method. efficiently catalyze 2-arylbenzimidazole, 2-arylbenzoxazole, 2-arylbenzothiazole alcohol, o-phenylenediamine, 2-aminophenol, 2-aminothiophenol, respectively, O2 without solvent additives. Comprehensive characterization revealed that possesses more oxygen vacancies stronger capture capability, promoting oxidation alcohol 2-aryl-2,3-dihydro-1H-benzimidazole. Due to its high density acidic sites, effectively boosts condensation cyclization aldehydes amines while simultaneously inhibiting formation diamines, thereby enhancing overall selectivity. Our work presents alternative green approach for industrial benzazoles.

Language: Английский

Citations

0