Journal of the American Chemical Society, Год журнала: 2024, Номер unknown
Опубликована: Ноя. 30, 2024
Due to the inherent challenges posed by linear coordination of gold(I) complexes, asymmetric gold-catalyzed processes remain challenging, particularly in atroposelective synthesis axially chiral skeletons. Except for extremely few examples intramolecular annulations, construction axial chirality via intermolecular alkyne transformation is still undeveloped. Herein, a gold/HNTf
Язык: Английский
Journal of the American Chemical Society, Год журнала: 2024, Номер 146(19), С. 13210 - 13225
Опубликована: Май 6, 2024
A new class of photoswitchable NHC ligands, named azImBA, has been developed by integrating azobenzene into a previously unreported imidazobenzoxazol-1-ylidene framework. These rigid photochromic carbenes enable precise control over confinement around metal's coordination sphere. As model system, gold(I) complexes these NHCs exhibit efficient bidirectional E–Z isomerization under visible light, offering versatile platform for reversibly photomodulating the reactivity organogold species. Comprehensive kinetic studies protodeauration reaction reveal rate differences up to 2 orders magnitude between E and Z isomers NHCs, resulting in quasi-complete visible-light-gated ON/OFF switchable system. Such high level photomodulation efficiency is unprecedented gold complexes, challenging current state-of-the-art organometallics. Thorough investigations ligand properties paired with structure–reactivity correlations underscored unique ligand's steric features as key factor reactivity. This effective photocontrol strategy was further validated catalysis, enabling situ photoswitching catalytic activity intramolecular hydroalkoxylation -amination alkynes. Given significance findings its potential widely applicable, easily customizable ancillary platform, azImBA poised stimulate development adaptive, multifunctional metal complexes.
Язык: Английский
Процитировано
6
European Journal of Organic Chemistry, Год журнала: 2023, Номер 27(4)
Опубликована: Ноя. 21, 2023
Abstract Although the asymmetric catalysis has made a spurt of progress, use chiral auxiliaries remains crucial in synthesis due to both reliability and versatility methods, predictability stereochemistry reactions. Up date, Evans’ non‐racemic oxazolidinone‐based synthetic methodology is still widely used synthesis. More importantly, Evans turned out be fruitful source inspiration for development related methodologies. However, although reviews on application organic medicinal chemistry continually appear literature, comprehensive review dedicating extensions elusive. In this review, we summarize methodology, which cover: (1) modification oxazolidinone auxiliaries; (2) extension aldol reaction from syn ‐aldol other diastereomeric adducts; (3) types; (4) imide‐type substrates N ‐alkenyl, ‐allenenyl ‐alkynyl oxazolidinones; (5) achiral catalysis; (6) catalytic transformation products; (7) straightforward transformations products classes compounds than carboxylic acids, esters, alcohols, Weinreb amides.
Язык: Английский
Процитировано
12
ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 6128 - 6136
Опубликована: Апрель 8, 2024
Fluorinated JohnPhos-type ligands are proposed as accelerating tools in homogeneous gold(I) catalysis, with PedroPhosAuCl (Cat1) the most efficient one. The well corresponding gold complexes were synthesized high yields and fully characterized also via single-crystal X-ray diffraction. A secondary interaction between distal phenyl ring of phosphane ligand metal center is identified key for fine-tuning overall catalytic performance complexes. In particular, kinetic computational analysis revealed that by accommodating F atoms on biphenyl pendant ligand, more reactive organo-gold intermediates realized toward subsequent nucleophilic condensations. gold-catalyzed indole-hydroarylation 1,6-enynes intramolecular hydroindolynation alkynes have been adopted benchmark reactions to exemplify these effects.
Язык: Английский
Процитировано
4
Chemical Communications, Год журнала: 2024, Номер unknown
Опубликована: Дек. 18, 2024
During the process of developing smart chiroptical luminophores, BODIPYs have emerged as candidates utmost importance. Here in we will discuss their synthesis.
Язык: Английский
Процитировано
2
ACS Applied Polymer Materials, Год журнала: 2024, Номер 6(5), С. 2453 - 2463
Опубликована: Фев. 15, 2024
Two microporous polymer networks having a confined AuI carbene catalyst were obtained and tested for the skeletal rearrangement of enynes. These catalysts from precursor porous organic polymers (POPs), type network, synthesized by reaction isatin or mixture isatin/trifluoroacetophenone (1:1) with triptycene (POP1 POP2, respectively) through an electrophilic aromatic substitution, EAS, promoted trifluoromethanesulfonic acid. precursors could be easily functionalized lactam moiety to form (POP1-AuCarbene POP2-AuCarbene). The carbenes proved very active dimethyl 2-(3-methyl-2-butenyl)-2-propinylmalonate enyne. A large increase in stability was observed compared those most homogeneous described so far bibliography. This long-term associated separation atoms, induced their confinement networks. In particular, POP2-AuCarbene exhibited outstanding stability, maintaining catalytic activity even after several months.
Язык: Английский
Процитировано
1
Organic Letters, Год журнала: 2024, Номер 26(30), С. 6375 - 6379
Опубликована: Июль 18, 2024
Acetylene has been underexploited despite being a highly valuable feedstock for chemical synthesis. We have developed the first true gold(I)-catalyzed intermolecular three-component reaction between acetylene, alkenes, and alcohols to afford β-vinyl hemiaminal scaffolds from N-vinyl amides. Unusual biscyclopropyl 3-vinyl N-heterocyclic were obtained through incorporation of second unit or tethered alkene into starting material.
Язык: Английский
Процитировано
1
Опубликована: Янв. 1, 2024
Язык: Английский
Процитировано
0
Tetrahedron, Год журнала: 2024, Номер unknown, С. 134257 - 134257
Опубликована: Сен. 1, 2024
Язык: Английский
Процитировано
0
Progress in heterocyclic chemistry, Год журнала: 2024, Номер unknown, С. 421 - 484
Опубликована: Янв. 1, 2024
Язык: Английский
Процитировано
0
Journal of the American Chemical Society, Год журнала: 2024, Номер unknown
Опубликована: Ноя. 30, 2024
Due to the inherent challenges posed by linear coordination of gold(I) complexes, asymmetric gold-catalyzed processes remain challenging, particularly in atroposelective synthesis axially chiral skeletons. Except for extremely few examples intramolecular annulations, construction axial chirality via intermolecular alkyne transformation is still undeveloped. Herein, a gold/HNTf
Язык: Английский
Процитировано
0