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

и другие.

ACS Catalysis, Год журнала: 2024, Номер 15(1), С. 370 - 380

Опубликована: Дек. 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.

Язык: Английский

Access to N-α-deuterated amino acids and DNA conjugates via Ca(II)-HFIP-mediated reductive deutero-amination of α-oxo-carbonyl compounds DOI Creative Commons
Haoran Li,

Yuwei Liu,

Silin Zhang

и другие.

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 20, 2025

The development of practical and selective strategies for deuterium incorporation to construct deuterated molecules, particularly deuterium-labeled amino acids, has become as a growing focus basic research, yet it remains formidable challenge. Herein, we present bioinspired calcium-HFIP-mediated site-selective reductive deutero-amination α-oxo-carbonyl compounds with amines. Utilizing d2-Hantzsch ester the source, this reaction attains remarkable deuteration efficiency (> 99% deuteration). It enables synthesis N-α-deuterated acid motifs wide range functionality, evidenced by over 130 examples. method exhibits compatibility diverse substrates, such peptides, drug natural products bearing different substituents. Moreover, application strategy in DNA-tagged acids/peptides been demonstrated. This work offers an efficient innovative solution chemistry holds substantial potential organic synthesis, medicinal chemistry, chemical biology.

Язык: Английский

Процитировано

1
Nitrene-mediated glycosylation with thioglycoside donors under metal catalysis DOI Creative Commons
Ziqian Bai, Zhiyi Wei, Shiyang Zhu

и другие.

Science Advances, Год журнала: 2025, Номер 11(8)

Опубликована: Фев. 21, 2025

Glycosylation chemistry plays a pivotal role in glycoscience. Recent substantial developments have poised the field to address emerging challenges related sustainability, cost efficiency, and robust applicability complex substrate settings. The transition from stoichiometric activation metal-catalyzed methods promises enhanced chemoselectivity greater precision controlling glycosidic bond breakage formation, key overcoming existing obstacles. Here, we report nitrene-mediated glycosylation strategy using regular aryl sulfide glycosyl donors easily accessible 3-methyl dioxazolone as an activator under catalysis of iron or ruthenium. iron-catalyzed system demonstrates exceptional catalytic reactivity, requiring little 0.1 mole % catalyst at room temperature, works well for peptide substrates. ruthenium-catalyzed can accommodate acid-sensitive functional groups challenging low-reactivity acceptors. Mechanistic investigations unveiled unusual multistep pathways involving sulfur imidation via nitrene transfer sulfur-to-oxygen rearrangement N-acyl sulfilimines donors.

Язык: Английский

Процитировано

1
Hydrogen-Bonding Network-Enabled Terminal Selective Heteroarylation of Allenamides in Hexafluoroisopropanol DOI
Sachin Balaso Mohite, Partha Sarathi Bera, Yafia Kousin Mirza

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

Hexafluoroisopropanol (HFIP)-mediated terminal selective heteroarylation of allenamides has been accomplished through H-bonding network-enabled substrate activation in a robust fashion. This strategy features cascade process involving sequential nucleophilic addition followed by electrophilic heteroaromatic substitution and is well suited for late-stage functionalization complex bioactive molecules. The elucidation the underlying mechanism was achieved comprehensive combination several control experiments, kinetic studies, isotopic labeling isolation HFIP-allenamide intermediate adduct.

Язык: Английский

Процитировано

1
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

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 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

Язык: Английский

Процитировано

4
HFIP-Promoted Aromatic Electrophilic Amidation of Indoles and Pyrroles with Isocyanates DOI
Liang-Bi Chen, Decheng Li, Hongye Wang

и другие.

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 19, 2025

A mild and practical method for synthesizing amidoindoles amidopyrroles was described via the direct amidation of indoles or pyrroles with isocyanates promoted by 1,1,1,3,3,3-hexafluoroisopropanol (HFIP). In this reaction, HFIP acted as a strong hydrogen bond-donating solvent to activate isocyanates, enabling electron-rich nitrogen-containing heterocycles.

Язык: Английский

Процитировано

0
Synthesis of N–H Aziridines from Unactivated Olefins Using Hydroxylamine-O-Sulfonic Acids as Aminating Agent DOI
Yi Huang, Shiyang Zhu, Gang He

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(9), С. 6263 - 6273

Опубликована: Апрель 23, 2024

Herein, we presented a practical methodology for the intermolecular aziridination of alkenes, using HOSA as aminating agent, alongside pyridine or piperidine base, within HFIP solvent system. Notably, this approach showcases excellent reactivity, especially with nonactivated and facilitates transformation various alkenes substrates, including mono-, di-, tri, tetra-substituted into aziridines moderate to yield. This method presents promising avenue synthesizing from wide range featuring benefits straightforward operation, mild reaction conditions, extensive substrate compatibility, scalability.

Язык: Английский

Процитировано

2
Brønsted Acid Catalyzed Dehydroxylative Cyanation of Benzylic Alcohols with Trimethylsilyl Cyanide Using 1,1,1,3,3,3‐Hexafluoro‐2‐propanol as a Solvent DOI
Kosho Makino,

Mai Hasebe,

Shunsuke Sueki

и другие.

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(25)

Опубликована: Май 7, 2024

Abstract A concise and direct Brønsted acid catalyzed cyanation of secondary tertiary benzylic allylic alcohols has been developed using trimethylsilyl cyanide (TMSCN) as a source 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) solvent. The present transition‐metal‐free catalytic process is operationally simple to perform under “open‐flask” conditions applicable the preparation number α‐arylacetonitriles well late‐stage material transformations. effectiveness protocol was further demonstrated by first enantioselective synthesis determination absolute configuration verimol F.

Язык: Английский

Процитировано

1
Calcium(II)-Catalyzed off-/on-DNA Reductive Deuteration Amination in HFIP: Modular Access to N-α-Deuterated Amino Acids DOI Creative Commons
Shengdong Wang, Haoran Li,

Yuwei Liu

и другие.

Research Square (Research Square), Год журнала: 2024, Номер unknown

Опубликована: Авг. 27, 2024

Abstract The development of practical and selective deuterium incorporation strategies for building deuterated molecules, especially deuterium-labeled amino acids, has become an increasing focus in basic research, but still remains challenging. We herein report a bioinspired calcium(II)/HFIP-catalyzed site-selective modular reductive deuteration amination simple keto acids/esters with amines by using d2-Hantzsch ester as the source, delivering N-α-deuterated acid motifs remarkable efficiency (>99 ratio) diverse functionality (>130 examples), which various substrates, including peptides, drug molecules natural products bearing different substituted forms, was found to be well compatible. Besides, application this strategy on-DNA synthesis DNA-tagged acids/peptides been exemplified. work provides efficient innovative solution chemistry should have robust potential organic synthesis, medicinal chemical biology.

Язык: Английский

Процитировано

1
Triflic Acid-Mediated Chemoselective Indole C2-Heteroarylation of Peptide Tryptophan Residues by Triazine DOI
Jian Li, Qi-Long Hu,

Jia-Shu Liu

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 9, 2024

Peptide modification provides opportunities to afford peptides with designed functions. Among the proteogenic amino acids, tryptophan represents an ideal and attractive target for peptide because of exclusive chemical reactivity its unique indole structure. Herein, we reported C2 position-selective transition-metal-free approach derivatives tryptophan-containing by triazine via triflic acid activation that incorporated functional group could act as orthogonal handle further bioconjugation inverse electron demand Diels–Alder reaction.

Язык: Английский

Процитировано

1
Transition-metal-free synthesis of triarylmethanes via Friedel-Crafts reactions of imidazo[1,2-a]pyridines with chlorohydrocarbon derivatives DOI Creative Commons

Xinlei Fu,

Longhui Wu,

Xiaohua Guo

и другие.

Journal of Saudi Chemical Society, Год журнала: 2024, Номер 28(4), С. 101883 - 101883

Опубликована: Май 29, 2024

A facile, transition-metal-free, HFIP-promoted method for the synthesis of triarylmethanes through direct Friedel-Crafts reactions imidazo[1,2-a]pyridines with chlorohydrocarbon derivatives has been described, which allows efficient containing in good to satisfactory yields at room temperature. This transformation features simple operation, excellent functional group tolerance, and a broad substrate scope.

Язык: Английский

Процитировано

0