Computational Study on the Inhibition Mechanisms of the Ziegler-Natta Catalyst in the Propylene Polymerization Process: Part 1 Effects of Acetylene and Methylacetylene.

Acetylene and methylacetylene are impurities commonly found in the raw materials used for the production of polymers such as polypropylene and polyethylene. Experimental evidence indicates that both acetylene and methylacetylene can decrease the productivity of the Ziegler-Natta catalyst and alter the properties of the resulting polymer. However, there is still a lack of understanding regarding the mechanisms through which these substances affect this process. Therefore, elucidating these mechanisms is crucial to develop effective solutions to this problem. In this study, the inhibition mechanisms of the Ziegler-Natta catalyst by acetylene and methylacetylene are presented and compared with the incorporation of the first propylene monomer (chain initiation) to elucidate experimental effects. The Density Functional Theory (DFT) method was used, along with the B3LYP-D3 functional and the 6-311++G(d,p) basis set. The recorded adsorption energies were -11.10, -13.99, and -0.31 kcal mol-1, while the activation energies were 1.53, 2.83, and 28.36 kcal mol-1 for acetylene, methylacetylene, and propylene, respectively. The determined rate constants were 4.68 × 1011, 5.29 × 1011, and 2.3 × 10-8 M-1 s-1 for acetylene, methylacetylene, and propylene, respectively. Based on these values, it is concluded that inhibition reactions are more feasible than propylene insertion only if an ethylene molecule has not been previously adsorbed, as such an event reinforces propylene adsorption.

Experimental and computational studies of steric factors in the isomerization of internal alkynes within the coordination environment of half-sandwich metal complexes.

The isomerization of internal alkynes Ar1C≡CAr2 within the coordination environment of low-valent half-sandwich [Ru(dppe)Cp]+ complexes via a 1,2-migration process affords vinylidene species [Ru{=C=C(Ar1)Ar2}(dppe)Cp]+. The rearrangement reactions of symmetrically and asymmetrically substituted substrates featuring different electron-donating and -withdrawing groups and of varying steric bulk were modelled using density functional theory (DFT), and the conclusions supported by experimental observations. Examination of the reaction pathway and associated activation barriers reveal a high solvent dependency for the generation of the key intermediate species [Ru(dppe)Cp]+ from [RuCl(dppe)Cp] by Na+ induced halide abstraction , with the lattice enthalpy of the NaCl by-product playing a critical role in the overall thermochemical balance of the reaction. The activation barriers associated with the reaction of [Ru(dppe)Cp]+ with Ar1C≡CAr2, and the relative energies of the alkyne complexes [Ru(h2-Ar1C≡CAr2)(dppe)Cp]+, are sensitive to the electron density of the alkyne and conformational changes associated with the 'bend-back' of the substrate. The latter differs by up to 66.1 kJ/mol, which in turn impacts the barrier height of the subsequent 1,2-migration step . The relative importance of these factors is evinced by the successful rearrangement of the very sterically congested 1(9-anthryl)-2(9-phenanthryl) acetylene into the fully characterized diaryl vinylidene complex, which was isolated in 89% yield.

An improved gold(I) catalytic system for the preparation of coumarins via intramolecular cyclization.

A catalytic system comprising a gold(I) complex with an N-heterocyclic carbene (NHC) ligand in an ionic liquid as solvent exhibits higher catalytic efficiency compared to state of the art systems in the title reaction, which enables using down to 0.01 mol% gold. A commercial gold(I) catalyst such as IPrAuNTf2 can be employed for this purpose. In the case of less reactive substrates bearing electron-withdrawing substituents at the phenol moiety, a tailor made NHC-gold(I) precatalyst exhibits improved reactivity and can be advantageously employed compared to the commercial one.

Glaser-Hay-Coupled Random Copolymers Containing Boron Difluoride Formazanate Dyes.

𝜋-Conjugated polymers, including those based on acetylenic repeating units, are an exciting class of materials that offer narrow optical band gaps and tunable frontier orbital energies that lead to their use in organic electronics. This work expands the knowledge of structure-property relationships of acetylenic polymers through the synthesis and characterization of a series of Glaser-Hay-coupled model compounds and random copolymers comprised of BF2 formazanate, fluorene, and/or bis(alkoxy)benzene units. The model compounds and copolymers synthesized exhibit redox activity associated with the reversible reduction of the BF2 formazanate units and the irreversible reduction of the fluorene and bis(alkoxy)benzene units. The copolymers exhibit absorption profiles characteristic or intermediate of their respective models and homopolymers, leading to broad absorption of UV-vis light. The alkyne linkages of the model compounds and copolymers are reacted with [Co2(CO)8] to convert the alkyne functional groups into cobalt carbonyl clusters. This transformation leads to blue-shifted absorption profiles due to a decrease in π-conjugation, demonstrating the ability to tune the properties of these materials through post-polymerization functionalization. The redox activity and broad absorption bands of the polymers reported make them excellent candidates for use in photovoltaics and other light-harvesting applications.

Access to Alkenyl Cyclobutanols by Ni-Catalyzed Regio- and Enantio-selective syn-Hydrometalative 4-exo-trig Cyclization of Alkynones.

Enantioselective synthesis of (spiro)cyclobutane derivatives poses significant challenges yet holds promising applications for both synthetic and medicinal chemistry. We report here a nickel-catalyzed asymmetric syn-hydrometalative 4-exo-trig cyclization of alkynones to synthesize alkenyl cyclobutanols with a tetrasubstituted stereocenter. This strategy features a broad substrate scope, delivering a variety of trifluoromethyl-containing rigid (spiro)carbocycle skeletons in good yields and high enantioselectivities (up to 84% yield and 98.5:1.5 er). The synthetic utility is demonstrated through stereospecific transformations into fused spirocycles. Experimental and computational mechanistic studies indicate that the reaction is initiated by an active Ni-H species, with carbonyl-directed hydrometalation as the key for regioselective control. This catalytic method provides a general solution for regioselective hydrofunctionalization of alkynes and represents an efficient reaction pattern for assembling highly strained enantioenriched bioisosteres.

L-Cysteine-Catalysed Hydration of Activated Alkynes.

Hydration reactions consist of the introduction of a molecule of water into a chemical compound and are particularly useful to transform alkynes into carbonyls, which are strategic intermediates in the synthesis of a plethora of compounds. Herein we demonstrate that L-cysteine can catalyse the hydration of activated alkynes in a very effective and fully regioselective manner to access important building blocks in synthetic chemistry such as ß-ketosulfones, amides and esters, in aqueous media. The mild reaction conditions facilitated the integration with enzyme catalysis to access chiral ß-hydroxy sulfones from the corresponding alkynes in a one-pot cascade process in good yields and excellent enantiomeric ratios. These findings pave the way towards establishing a general method for metal-free, cost-effective, and more sustainable alkyne hydration processes.

Intermolecular 1,2-Aminoboration of Alkynes and the Critical Role of Electron-Rich Alkynes.

The intramolecular 1,2-aminoboration of alkynes by aminoboranes is rare and invariably requires a catalyst to proceed, while the intermolecular aminoboration of alkynes is yet entirely unknown. Through an exploration of the significance of electronics in alkynes for activating the B-N σ-bond of aminoboranes, we demonstrate in this work the first intermolecular 1,2-aminoboration of alkynes. These reactions employ a series of (amino)dihaloboranes and aminoboronic esters, mild reaction conditions, and no catalysts, yielding syn-addition alkene products with incorporation of two crucial functionalities: amino and boryl. While highly electron-rich examples can afford the aminoborated products (Z)-2-borylethenamines, other alkynes, including unactivated and less electron-rich examples, do not lead to the corresponding aminoborated products due to the fundamental impediment that the reactions are significantly endergonic.

One-Pot Transition-Metal-Free Synthesis of Alkynyl Amides.

Alkynyl amides play crucial roles in organic synthesis in the production of bioactive compounds and valuable heterocycles. Despite numerous studies on their synthesis, challenges persist due to the necessity of harsh or hazardous conditions and the use of costly or unstable reagents. Herein, we present a one-pot method for the synthesis of all three bonds of the alkyne under transition-metal free conditions. An important feature of this chemistry is the use of readily available feedstock chemicals, such as methyl esters and acetamides. This approach offers efficient access to a wide range of aryl and alkyl alkynyl amides and demonstrates excellent tolerance towards various functional groups in a sustainable and cost-effective manner.

The role of linkers and frustrated lewis pairs catalysts in the formation of zwitterionic 1,2-anti-addition product with non-conjugated terminal diacetylenes: A computational study.

This study presents a computational investigation into the mechanistic pathway and the linker units involved in forming the zwitterionic 1,2-anti-addition product of non-conjugated diacetylenes, di(propargyl)ether (DPE), di(prop-2yn-1yl)sulfane (DPS) and 1,6-Heptadiyne (HD) catalyzed by the inter-molecular phosphine/borane frustrated Lewis pairs (FLPs), i.e., PPh2[C6H3(CF3)2](P-CF)/[B(C6F5)3]([B]) and P(o-tolyl)3(P-tol)/[B(C6F5)3]([B]). The potential energy surface (PES) calculations reveal that the anti-addition of P-CF to the internal C-atoms of acetylene units is energetically more favored than that of the addition of P-tol in DPE, DPS, and HD by ∼10.0, ∼9.2, and ∼6.0 kcal/mol, respectively. The calculations performed with DPE contain "-O-," linker unit exhibits superior reactivity than DPS and HD, which suggests the electronegativity of linkers plays a significant role and facilitates the addition of Lewis bases. The higher electronegativity of linker units enables the 1,2-addition reaction by lowering the free energy activation barriers, as observed in the DFT calculations. The Molecular Electrostatic Potential (MESP) study shows that the electrostatic interactions favor the addition of P-CF to the active acetylene positions (C5/C4/C4) of [B]-DPE/DPS/HD-π complexes than the P-tol. The Distortion/Interaction (D/I) analysis reveals that transition states involving P-CF (TS1, TS3, and TS5) exhibit more interaction energy (ΔEInt) and less distortion energies (ΔEd) than that of the P-tol (TS2, TS4, and TS6). Further, the Energy Decomposition Analysis (EDA) also rationalizes the preferential approach of the electron-deficient Lewis base over the electron-rich one on the basis of the significant contribution of orbital interaction energies (ΔEorbital) in the cases of P-CF; TS1, TS3, and TS5. This study suggests that the electronic effects of substrates and the FLPs are crucial to facilitate the desired products formed with non-conjugated terminal alkynes.

Dirhodium(II)/ XantPhos Catalyzed Synthesis of ß-(E)-Vinylsilanes via Hydrosilylation and Isomerization from Alkynes.

A concise hydrosilylation of alkynes for synthesizing ß-(E)-vinylsilanes catalyzed by dirhodium(II)/XantPhos has been developed. In this reaction, ß-(E)-vinylsilanes were generated from the isomerization of ß-(Z)-vinylsilanes catalyzed by dirhodium(II) hydride species rather than the direct insertion of triple bond into M-H or M-Si bond (traditional Chalk-Harrod mechanism or modified Chalk-Harrod mechanism). The hydrosilylation displayed a broad substrate scope for alkynes and tertiary silanes, tolerating diverse functional groups including halides, nitrile, amines, esters, and heterocycles.

Advancement in Synthetic Strategies of Phosphorus Heterocycles: Recent Progress from Synthesis to Emerging Class of Optoelectronic Materials.

Organophosphorus heterocycles have long been acknowledged for their significant potential across diverse fields, including catalysis, material science, and drug development. Incorporating phosphorus functionalities into organic compounds offers a means to effectively tailor their medicinal properties, augment biological responses, and enhance selectivity and bioavailability. The distinctive physical and photoelectric characteristics of phosphorus-containing conjugated compounds have garnered considerable interest as promising materials for organic optoelectronics. These compounds find extensive utility in various applications such as light-emitting diodes, photovoltaic cells, phosphole-based fluorophores, and semiconductors.

Oxysulfonylation of Alkynes with Sodium Sulfinates to Access ß-Keto Sulfones Catalyzed by BF3·OEt2.

An efficient and operationally simple method for the synthesis of ß-keto sulfones through the BF3·OEt2-promoted reaction of alkynes and sodium sulfinates is developed. With its facile and selective access to the targets, it features good functional group compatibility, mild conditions, easily available starting materials, and good yields. Notably, the reaction does not require metal catalysts or chemical reagents with pungent odors.

Metal-Free, PPA-Mediated Fisher Indole Synthesis via Tandem Hydroamination-Cyclization Reaction between Simple Alkynes and Arylhydrazines.

A new variant of Fisher indole synthesis involving Bronsted acid-catalyzed hydrohydrazination of unactivated terminal and internal acetylenes with arylhydrazines is reported. The use of polyphosphoric acid alone either as the reaction medium or in the presence of a co-solvent appears to provide the required balance for activating the C-C triple bond towards the nucleophilic attack of the hydrazine moiety without unrepairable reactivity loss of the latter due to competing amino group protonation. Additionally, the formal hydration of acetylenes to the corresponding ketones occurs under the same conditions, making it an alternative approach for generating carbonyl groups from alkynes.

Dynamically Precise Constructing Dual-Atom Pd2 Catalyst:A Monodisperse Catalyst With High Stability for Semi-Hydrogenation of Alkyne.

Dual-atom catalysts (DACs) originate unprecedented reactivity and maximize resource efficiency. The fundamental difficulty lies in the high complexity and instability of DACs, making the rational design and targeted performance optimization a grand challenge. Here, an atomically dispersed Pd2 DAC with an in situ generated Pd─Pd bond is constructed by a dynamic strategy, which achieves high activity and selectivity for semi-hydrogenation of alkynes and functional internal acetylene, twice higher than commercial Lindlar catalyst. Density functional theory calculations and systematic experiments confirms the ultrahigh properties of Pd2 DAC originates from the synergistic effect of the dynamically generated Pd─Pd bonds. This discovery highlights the potential for dynamic strategies and opens unprecedented possibilities for the preparation of robust DACs on an industrial scale.

Differential Activation of Alkynes between Capped and Naked Ag Nanoclusters Anchored by Highly-Open Mesoporous CeO2 for Two Coupling Reactions with CO2.

The cyclization of 3-hydroxy alkynes and the carboxylation of terminal alkynes both with CO2 are two attractive strategies to simultaneously reduce CO2 emission and produce value-added chemicals. Herein, the differential activation of alkynes over atomically precise Ag nanoclusters (NCs) supported on Metal-organic framework-derived highly-open mesoporous CeO2 (HM-CeO2) by reserving or removing their surface captopril ligands is reported. The ligand-capped Ag NCs possess electron-rich Ag atoms as efficient π-activation catalytic sites in cyclization reactions, while the naked Ag NCs possess partial positive-charged Ag atoms as perfect σ-activation catalytic sites in carboxylation reactions. Impressively, via coupling with HM-CeO2 featuring abundant basic sites and quick mass transfer, the ligand-capped Ag NCs afford 97.9% yield of 4,4-dimethyl-5-methylidene-1,3-dioxolan-2-one for the cyclization of 2-methyl-3-butyn-2-ol with CO2, which is 4.5 times that of the naked Ag NCs (21.7%), while the naked Ag NCs achieve 98.5% yield of n-butyl 2-alkynoate for the carboxylation of phenylacetylene with CO2, which is 15.6 times that of ligand-capped Ag NCs (6.3%). Density functional theory calculations reveal the ligand-capped Ag NCs can effectively activate alkynyl carbonate ions for the intramolecular ring closing in cyclization reaction, while the naked Ag NCs are highly affiliative in stabilizing terminal alkynyl anions for the insertion of CO2 in carboxylation reaction.

Iodine-Catalyzed Carbonyl-Alkyne Metathesis Reactions.

The reaction between aldehydes or ketones and alkynes-the carbonyl-alkyne metathesis-constitutes a very useful strategy for the synthesis of α,ß-unsaturated carbonyls. We now demonstrate that iodine is a highly efficient catalyst for both the intra- and intermolecular metathesis reaction in very small concentrations (0.1-1 mol %). Our protocol outperforms other catalytic systems, is operationally very simple, cheap, metal-free, and tolerates a large variety of functional groups (e. g., -CN, -CO2Me, -Br, -OH) at very low catalyst loadings. We can furthermore show that iodine-catalyzed carbonyl-alkyne metatheses can be combined with other iodine-catalyzed reactions in one-pot procedures to afford larger and more complex molecular structures. Finally, our mechanistic studies indicate that the iodonium ion is the active catalyst under the reaction conditions.

Synthesis and optical properties of bis- and tris-alkynyl-2-trifluoromethylquinolines.

Three bis- or tris-brominated 2-trifluoromethylquinolines have been successfully applied in palladium-catalysed Sonogashira reactions, leading to several examples of alkynylated quinolines in good to excellent yields. Optical properties of selected products have been studied by steady state absorption and fluorescence spectroscopy which give insights of the influence of the substitution pattern and of the type of substituents on the optical properties.

Copper-Catalyzed Regiodivergent Asymmetric Difunctionalization of Terminal Alkynes.

We herein describe the first example of ligand-controlled, copper-catalyzed regiodivergent asymmetric difunctionalization of terminal alkynes through a cascade hydroboration and hydroallylation process. The catalytic system, consisting of (R)-DTBM-Segphos and CuBr, could efficiently achieve asymmetric 1,1-difunctionalization of aryl terminal alkynes, while ligand switching to (S,S)-Ph-BPE could result in asymmetric 1,2-difunctionalization exclusively. In addition, alkyl substituted terminal alkynes, especially industrially relevant acetylene and propyne, were also valid feedstocks for asymmetric 1,1-difunctionalization. This protocol is characterized by good functional group tolerance, a broad scope of substrates (>150 examples), and mild reaction conditions. We also showcase the value of this method in the late-stage functionalization of complicated bioactive molecules and simplifying the synthetic routes toward the key intermediacy of natural product (bruguierol A). Mechanistic studies combined with DFT calculations provide insight into the mechanism and origins of this ligand-controlled regio- and stereoselectivity.

BioLindlar Catalyst: Ene-Reductase-Promoted Selective Bioreduction of Cyanoalkynes to Give (Z)-Cyanoalkenes.

The direct synthesis of alkenes from alkynes usually requires the use of transition-metal catalysts. Unfortunately, efficient biocatalytic alternatives for this transformation have yet to be discovered. Herein, the selective bioreduction of electron-deficient alkynes to alkenes catalysed by ene-reductases (EREDs) is described. Alkynes bearing ketone, aldehyde, ester, and nitrile moieties have been effectively reduced with excellent conversions and stereoselectivities, observing clear trends for the E/Z ratios depending on the nature of the electron-withdrawing group. In the case of cyanoalkynes, (Z)-alkenes were obtained as the major product, and the reaction scope was expanded to a wide variety of aromatic substrates (up to >99 % conversion, and Z/E stereoselectivities of up to >99/1). Other alkynes containing aldehyde, ketone, or ester functionalities also proved to be excellent substrates, and interestingly gave the corresponding (E)-alkenes. Preparative biotransformations were performed on a 0.4 mmol scale, producing the desired (Z)-cyanoalkenes with good to excellent isolated yields (63-97 %). This novel reactivity has been rationalised through molecular docking by predicting the binding poses of key molecules in the ERED-pu-0006 active site.

Migration of Condensed Aromatic Hydrocarbons During Alkyne-Vinylidene Rearrangements.

Diarylacetylenes ArC≡CAr featuring condensed aromatic hydrocarbon fragments (Ar) such as naphthalene, anthracene, phenanthrene and pyrene were converted into vinylidene ligands by 1,2-migration reactions within the coordination sphere of half-sandwich complexes [MII(dppe)Cp]+ (MII = RuII, FeII). Comparison of the extent of conversion of the alkyne substrates to the vinylidene complexes [Ru{=C=CAr2}(dppe)Cp]+ with those obtained from acetylenes functionalized by smaller groups (H, CH3, Ph) show that the molecular volume (VM) of the migrating group and relief of steric congestion plays a role during the rearrangement process. Conversely, the H-atoms from the larger condensed ring aryl groups that are in close proximity to the migrating sites also have a significant influence on the efficacy and extent of the reaction by restricting access of the alkyne to the metal center, resulting in a less effective migration reaction. This combination of competing steric factors (acceleration due to relief of steric congestion and restricted access of the alkyne moiety to the reaction site) is exemplified by the facile migration of 1-pyryl entities and the low yields of vinylidene products formed from 1,2-bis(9-anthryl)acetylene.