Unraveling Alcohol Additive Effects on Hypervalent Iodine(III)-Catalyzed Asymmetric Phenolic Dearomatization: Ligand Substitution and Low-Barrier Hydrogen Bonds DOI
Hanliang Zheng, Cai Liu,

Xiaoyu Lai

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 370 - 380

Published: Dec. 18, 2024

Despite the widespread use of hexafluoropropanol (HFIP) as a "magic" solvent or additive in organic synthesis, its fundamental mechanisms lag far behind. This study presents mechanistic insights into puzzling alcohol effects observed Ishihara's conformationally flexible C2-symmetric iodoarene-catalyzed asymmetric phenolic dearomatization through density functional theory calculations. The results reveal that due to "booster effect" fluorinated alcohols, HFIP assembles trimeric hydrogen bond cluster displaces ligand from active iodine(III) catalyst and forms low-barrier with substrate, which significantly enhances oxidizing power center, thus facilitating electron-deficient phenols. Conversely, methanol is found promote electron-rich phenols via formally similar yet distinct mechanism, highlighting unique role an additive. gained this investigation advance our molecular-level understanding synergistic interactions between catalysts additives, potentially guiding design catalytic systems exploit these for broader applications.

Language: Английский

Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation DOI Creative Commons
Xinyu Zhang,

Deng Zhu,

Ren‐Fei Cao

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 15, 2024

Inherently chiral calixarenes hold great potential for applications in recognition, sensing, and asymmetric catalysis due to their unique structures. However, special structures relatively large sizes, the catalytic synthesis of inherently is challenging with very limited examples available. Here, we present an efficient method enantioselective sulfur-containing calix[4]arenes through desymmetrizing electrophilic sulfenylation calix[4]arenes. This reaction enabled by a 1,1'-binaphthyl-2,2'-diamine-derived sulfide catalyst hexafluoroisopropanol. Various are obtained moderate excellent yields high enantioselectivities. Control experiments indicate that thermodynamically favored C-SAr product formed from kinetically N-SAr combination hexafluoroisopropanol crucially important both enantioselectivity reactivity. Due authors report

Language: Английский

Citations

5
Ring-closing Disulfenylation of Alkenoic Thioester DOI Creative Commons

Kanaru Sasaki,

Miari Kurihara,

Hiroki Shigehisa

et al.

Published: Aug. 8, 2024

This study demonstrated for the first time that alkenoic thioesters can be effectively used as nucleophiles in ring-closing disulfenylation reactions. Our investigation revealed reaction hexafluoroisopropanol with an electrophilic sulfur reagent significantly enhances product yield. We gathered experimental and theoretical evidence to support superiority of over traditionally benzyl sulfide. Additionally, we explored substrate scope identified various factors affecting selectivity

Language: Английский

Citations

2
Ring-Closing Disulfenylation of Alkenoic Thioester DOI

Kanaru Sasaki,

Miari Kurihara,

Hiroki Shigehisa

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 26, 2024

This study demonstrated for the first time that alkenoic thioesters can be effectively used as nucleophiles in ring-closing disulfenylation reactions. Our investigation revealed reaction hexafluoroisopropanol with an electrophilic sulfur reagent significantly enhances product yield. We gathered experimental and theoretical evidence to support superiority of over traditionally benzyl sulfide. Additionally, we explored substrate scope identified various factors affecting selectivity

Language: Английский

Citations

1
A 1,2-Aryl Migration Reaction in Visible-Light-Mediated Synthesis of Quinoxaline Derivatives: Mechanistic Studies DOI
Tuan H. Ho, Binh Khanh, Tuong Anh To

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 4, 2024

The synthesis of quinoxaline derivatives holds critical importance in various fields ranging from pharmaceuticals to material science. In this study, we introduce a practical light-mediated method for the efficient derivatives. This approach enabled sequential two-step, one-pot 1,2-dihydro-2,2-diaryl-substituted quinoxalines quinones, alkynes, and diamines. By adjusting stoichiometric ratios reaction conditions, was shifted yield 2,3-diaryl-substituted exclusively, demonstrating remarkable versatility efficiency. switch outcomes revealed involve an oxidative 1,2-aryl migration through combination thorough experimental computational mechanistic studies.

Language: Английский

Citations

1
Contents list DOI Creative Commons
Takahiro Ichikawa, Takeshi Yamada,

Nanami Aoki

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(19), P. 6983 - 6993

Published: Jan. 1, 2024

Citations

0
Chlorocyclization of Alkenoic Thioester DOI Open Access

Miari Kurihara,

Kanaru Sasaki,

Hiroki Shigehisa

et al.

Chemical and Pharmaceutical Bulletin, Journal Year: 2024, Volume and Issue: 72(11), P. 1034 - 1037

Published: Nov. 29, 2024

This study introduces a novel method for ring-closing chlorosulfenylation of alkenoic thioesters using N-chlorosuccinimide in hexafluoroisopropanol under mild conditions. reaction efficiently forms five-membered cyclic sulfur compounds with high selectivity, representing significant advancement the synthesis chlorinated S-heterocycles. Computational analysis density functional theory demonstrates superiority thioester nucleophiles over traditional benzyl sulfides this reaction, highlighting energetic preference thioesters.

Language: Английский

Citations

0
Unraveling Alcohol Additive Effects on Hypervalent Iodine(III)-Catalyzed Asymmetric Phenolic Dearomatization: Ligand Substitution and Low-Barrier Hydrogen Bonds DOI
Hanliang Zheng, Cai Liu,

Xiaoyu Lai

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 370 - 380

Published: Dec. 18, 2024

Despite the widespread use of hexafluoropropanol (HFIP) as a "magic" solvent or additive in organic synthesis, its fundamental mechanisms lag far behind. This study presents mechanistic insights into puzzling alcohol effects observed Ishihara's conformationally flexible C2-symmetric iodoarene-catalyzed asymmetric phenolic dearomatization through density functional theory calculations. The results reveal that due to "booster effect" fluorinated alcohols, HFIP assembles trimeric hydrogen bond cluster displaces ligand from active iodine(III) catalyst and forms low-barrier with substrate, which significantly enhances oxidizing power center, thus facilitating electron-deficient phenols. Conversely, methanol is found promote electron-rich phenols via formally similar yet distinct mechanism, highlighting unique role an additive. gained this investigation advance our molecular-level understanding synergistic interactions between catalysts additives, potentially guiding design catalytic systems exploit these for broader applications.

Language: Английский

Citations

0