Two new Zn(II) complexes with tridentate hydrazone-based ligands (condensation products of 2-acetylthiazole) were synthesized and characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy and single crystal X-ray diffraction methods. The complexes 1, 2 and recently synthesized [ZnL3(NCS)2] (L3 = (E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethan-1-aminium) complex 3 were tested as potential catalysts for the ketone-amine-alkyne (KA2) coupling reaction. The gas-phase geometry optimization of newly synthesized and characterized Zn(II) complexes has been computed at the density functional theory (DFT)/B3LYP/6–31G level of theory, while the highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO and LUMO) energies were calculated within the time-dependent density functional theory (TD-DFT) at B3LYP/6-31G and B3LYP/6-311G(d,p) levels of theory. From the energies of frontier molecular orbitals (HOMO–LUMO), the reactivity descriptors, such as chemical potential (μ), hardness (η), softness (S), electronegativity (χ) and electrophilicity index (ω) have been calculated. The energetic behavior of the investigated compounds (1 and 2) has been examined in gas phase and solvent media using the polarizable continuum model. For comparison reasons, the same calculations have been performed for recently synthesized [ZnL3(NCS)2] complex 3. DFT results show that compound 1 has the smaller frontier orbital gap so, it is more polarizable and is associated with a higher chemical reactivity, low kinetic stability and is termed as soft molecule.
Au nanoparticles supported on TiO 2 (1 mol %) catalyze the quantitative cycloisomerization of conjugated allenones into furans under very mild conditions. The reaction rate is accelerated by adding acetic acid (1 equiv), but the acid does not participate in the protodeauration step as in the corresponding Au(III)-catalyzed transformation. The process is purely heterogeneous, allowing thus the recycling and reuse of the catalyst effectively in several runs.
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Recyclable supported Au nanoparticles on TiO2 catalyze the cyclization of N‐propargyl or N‐homopropargyl β‐enaminones followed by dehydrogenation (aromatization) leading to substituted 3‐keto pyridines or 4‐picolines in very good yields. This pathway is in contrast to their known cyclization in the presence of Au(I) or Au(III) catalysts which provides 1,4‐oxazepines, instead. The enaminones are formed in situ upon mixing a conjugated allenone or allenyl ester with the alkynylamine, thus the pyridine‐forming transformation is typically a one pot process.
A straightforward,
user-friendly, efficient protocol for the one
pot, ZnI
2
-catalyzed allenylation of terminal alkynes with
pyrrolidine and ketones, toward trisubstituted allenes, is described.
Trisubstituted allenes can be obtained under either conventional heating
or microwave irradiation conditions, which significantly reduces the
reaction time. A sustainable, widely available, and low-cost metal
salt catalyst is employed, and the reactions are carried out under
solvent-free conditions. Among others, synthetically valuable allenes
bearing functionalities such as amide, hydroxyl, or phthalimide can
be efficiently prepared. Mechanistic experiments, including kinetic
isotope effect measurements and density functional theory (DFT) calculations,
suggest a rate-determining [1,5]-hydride transfer during the transformation
of the intermediate propargylamine to the final allene.
Despite the unique position of gold catalysis in contemporary organic synthesis, this area of research is notorious for requiring activators and/or additives that enable catalysis by generating cationic forms of gold catalysts. Cycloisomerization reactions occupy a significant portion of the gold-catalyzed reaction space, while they represent a diverse family of reactions that are frequently utilized in synthesis. Herein, hexafluoroisopropanol (HFIP) is shown to be a uniquely simple tool for gold-catalyzed cycloisomerizations, rendering the use of external activators obsolete and leading to highly active catalytic systems with ppm levels of catalyst loading in certain cases. HFIP assumes a dual role as a solvent and an activator, operating via the dynamic activation of the Au−Cl bond through hydrogen bonding, which initiates the catalytic cycle. This special mode of catalysis can enable efficient and scalable cyclization reactions of propargylamides and ynoic acids with simple [AuCl(L)] complexes. A thorough screening of ancillary ligands and counter anions has been performed, establishing this methodology as an alternative to elaborate ligand/catalyst design and to the use of activators. Additionally, this concept is applied in C−C bond-forming cycloisomerization reactions leading to 2H-chromenes and to the design of catalytic systems for sequential or one-pot transformations leading to activated ketoesters, a functionalized N-heterocyclic carbene (NHC) precursor salt, and a compound bearing the bioactive indole core, among others. Importantly, through mechanistic investigations, including a "snapshot" of the species of interest in the solid state, we were able to unambiguously detect the key H-bonding interaction between HFIP and the gold catalyst, shedding light on the intermolecular mode of activation that enables catalysis. In the cases examined herein, HFIP is not only an excellent solvent but also a potent activator and a valuable synthetic handle when incorporated into functional groups of products.
Despite the unique position of gold catalysis in contemporary organic synthesis, this area of research is notorious for requiring activators and/or additives that enable catalysis by generating cationic forms of gold catalysts. Cycloisomeriza-tion reactions occupy a significant portion of the gold-catalyzed reaction space, while they represent a diverse family of reactions which are frequently utilized in synthesis. Herein, hexafluoroisopropanol (HFIP) is shown to be a uniquely simple tool for gold-catalyzed cycloisomerizations, rendering the use of external activators obsolete, and leading to high-ly active catalytic systems with ppm levels of catalyst loading in certain cases. HFIP assumes a dual role as solvent and activator, operating via the dynamic activation of the Au-Cl bond through hydrogen bonding, which initiates the catalytic cycle. This special mode of catalysis can enable efficient and scalable cyclization reactions of propargylamides and ynoic acids with simple [AuCl(L)] complexes. A thorough screening of ancillary ligands and counter anions has been per-formed, establishing this methodology as an alternative to elaborate ligand/catalyst design and to the use of activators. Additionally, this concept is applied in C-C bond forming cycloisomerization reactions leading to 2H-chromenes and to the design of catalytic systems for sequential or one-pot transformations leading to activated ketoesters, a functionalized N-heterocyclic carbene (NHC) precursor salt, and a compound bearing the bioactive indole core, among others. Im-portantly, through mechanistic investigations including a “snapshot” of the species of interest in the solid state, we were able to unambiguously detect the key H-bonding interaction between HFIP and the gold catalyst, shedding light on the intermolecular mode of activation that enables catalysis. In the cases examined herein, HFIP is not only an excellent sol-vent, but also a potent activator and a valuable synthetic handle when incorporated into functional groups of products.
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