Leveraging Electron Push-Pull Effect for Catalytic Polymerization and Degradation of a Cyclobutane Monomer System.

Ring-opening polymerization (ROP) offers a striking solution to solve problems encountered in step-growth condensation polymerization, including precise control over molecular weight, molecular weight distribution, and topology. This has inspired our interest in ROP of cycloalkanes with an ultimate goal to rethink polyolefins, which clearly poses a number of challenges. Practicality of ROP of cycloalkanes is actually limited by their low polymerizability and elusive mechanisms which arise from significantly varied ring size and non-polar C-C bonds in monomers. In this work, by using Lewis acid/Brønsted base/C(sp3)-H initiator system previously developed in our laboratory, we focus on cyclobutanes and explore the positional and electronic effects of substituents on the ring, namely electron push-pull effect, in promoting controlled polymerization to afford densely functionalized poly(cyclobutanes), as well as catalytic degradation of obtained polymers for upcycling. More importantly, experiments and DFT calculations unveil considerable population of Lewis-acid-induced thermostabilized 1,4-zwitterions, which distinguish cyclobutanes from cyclopropanes and others. All these findings would shed light on catalytic synthesis and degradation of saturated all-carbon main-chain polymers, as well as small molecule transformations of cyclobutanes.

ReaLigands: A Ligand Library Cultivated from Experiment and Intended for Molecular Computational Catalyst Design.

Computational catalyst design requires identification of a metal and ligand that together result in the desired reaction reactivity and/or selectivity. A major impediment to translating computational designs to experiments is evaluating ligands that are likely to be synthesized. Here, we provide a solution to this impediment with our ReaLigands library that contains >30,000 monodentate, bidentate (didentate), tridentate, and larger ligands cultivated by dismantling experimentally reported crystal structures. Individual ligands from mononuclear crystal structures were identified using a modified depth-first search algorithm and charge was assigned using a machine learning model based on quantum-chemical calculated features. In the library, ligands are sorted based on direct ligand-to-metal atomic connections and on denticity. Representative principal component analysis (PCA) and uniform manifold approximation and projection (UMAP) analyses were used to analyze several tridentate ligand categories, which revealed both the diversity of ligands and connections between ligand categories. We also demonstrated the utility of this library by implementing it with our building and optimization tools, which resulted in the very rapid generation of barriers for 750 bidentate ligands for Rh-hydride ethylene migratory insertion.

C-H Insertion in Dirhodium Tetracarboxylate-Catalyzed Reactions despite Dynamical Tendencies toward Fragmentation: Implications for Reaction Efficiency and Catalyst Design.

Rh-catalyzed C-H insertion reactions to form ß-lactones suffer from post-transition state bifurcations, with the same transition states leading to ketones and ketenes via fragmentation in addition to ß-lactones. In such a circumstance, traditional transition state theory cannot predict product selectivity, so we employed ab initio molecular dynamics simulations to do so and provide a framework for rationalizing the origins of said selectivity. Weak interactions between the catalyst and substrate were studied using energy decomposition and noncovalent interaction analyses, which unmasked an important role of the 2-bromophenyl substituent that has been used in multiple ß-lactone-forming C-H insertion reactions. Small and large catalysts were shown to behave differently, with the latter providing a means of overcoming dynamically preferred fragmentation by lowering the barrier for the recombination of the product fragments in the grip of the large catalyst active site cavity.

Theory and Experiment Demonstrate that Sb(V)-Promoted Methane C-H Activation and Functionalization Outcompete Superacid Protonolysis in Sulfuric Acid.

Sb(V) in strong Brønsted acid solvents is traditionally assumed to react with light alkanes through superacid protonolysis, which results in carbocation intermediates, H2, and carbon oligomerization. In contrast to this general assumption, our density functional theory (DFT) calculations revealed an accessible barrier for C-H activation between methane and Sb(V) in sulfuric acid that could potentially outcompete superacid protonolysis. This prompted us to experimentally examine this reaction in sulfuric acid with oleum, which has never been reported because of presumed superacid reactivity. Reaction of methane at 180 °C for 3 h resulted in very high yields of methyl bisulfate without significant overoxidation. Our DFT calculations show that a C-H activation and Sb-Me bond functionalization mechanism to give methyl bisulfate outcompetes methane protonolysis and many other possible reaction mechanisms, such as electron transfer, proton-coupled electron transfer, and hydride abstraction. Our DFT calculations also explain experimental hydrogen-deuterium exchange studies and the absence of methane carbo-functionalization/oligomerization products. Overall, this work demonstrates that in very strong Brønsted acid solvent, Sb(V) can induce innersphere reaction mechanisms akin to transition metals and outcompete superacid reactivity.

Effects of electrostatic drag on the velocity of hydrogen migration - pre- and post-transition state enthalpy/entropy compensation.

Ab initio molecular dynamics calculations were used to explore the underlying factors that modulate the velocity of hydrogen migration for 1,2 hydrogen shifts in carbocations in which different groups interact noncovalently with the migrating hydrogen. Our results indicate that stronger electrostatic interactions between the migrating hydrogen and nearby π-systems lead to slower hydrogen migration, an effect tied to entropic contributions from the hydrogen + neighboring group substructures.

Nucleophile Coordination Enabled Regioselectivity in Palladium-Catalyzed Asymmetric Allylic C-H Alkylation.

Branched selectivity in asymmetric allylic C-H alkylation is enabled by using 2-acylimidazoles as nucleophiles in the presence of a chiral phosphoramidite-palladium catalyst. A wide range of terminal alkenes, including 1,4-dienes and allylarenes, are nicely tolerated and provide chiral 2-acylimidazoles in moderate to high yields and with high levels of regio-, and enantio-, and E/Z-selectivities. Mechanistic studies using density-functional theory calculations suggest a nucleophile-coordination-enabled inner-sphere attack mode for the enantioselective carbon-carbon bond-forming event.

Lewis Base/Copper Cooperatively Catalyzed Asymmetric α-Amination of Esters with Diaziridinone.

An enantioselective α-amination of esters by a Lewis base/copper(I) cooperative catalysis strategy has been developed. The transient chiral C1-ammonium enolate generated from pentafluorophenyl ester and nucleophilic Lewis base is nicely compatible with the copper intermediate formed from N, N-di- t-butyldiaziridinone and Cu(I) to allow for high levels of stereochemical control. The cooperative catalytic reaction leads to a diverse set of highly enantioenriched hydantoins in good yields with excellent enantioselectivities (90-99% ee).

Palladium-Catalyzed Cascade sp2 C-H Functionalization/Intramolecular Asymmetric Allylation: From Aryl Ureas and 1,3-Dienes to Chiral Indolines.

A chiral PdII -catalyzed cascade sp2 C-H functionalization/intramolecular asymmetric allylation reaction is reported. A new chiral sulfoxide-oxazoline (SOX) ligand bearing single chiral center on the sulfur was identified as the optimal ligand for the reaction, being efficient both in the C-H cleavage step and the stereocontrol of the allylation step. The broad scope of this method with respect to aryl ureas and 1,3-dienes enables the rapid construction of valuable chiral indoline derivatives with high yields and enantioselectivities (up to 99 % yield, up to 95:5 e.r.).

Palladium-Catalyzed Enantioselective Heteroannulation of 1,3-Dienes by Functionally Substituted Aryl Iodides.

The first enantioselective heteroannulation of 1,3-dienes by 2-iodoanilines and 2-iodobenzylic alcohols is described. The application of a BINOL-derived phosphoramidite ligand bearing electron-withdrawing substituents is the key to obtaining high enantioselectivity. This protocol provides an efficient way to access optically active chiral indolines and isochromans from readily available starting materials.

Enantioselective construction of [6,5,6]-carbocyclic systems by organo/metal-catalyzed sequential reactions.

An efficient strategy for the enantioselective construction of [6,5,6]-carbocyclic compounds has been established via one-pot reaction of (E)-4-(2-ethynylphenyl)but-3-en-2-ones with maleimide sequentially catalyzed by cinchona alkaloid-based primary amine and gold complex (Ph3PAuNTf2). This methodology provided a facile approach to access the [6,5,6]-tricyclic skeleton in fairly good yield and with perfect enantioselectivities (98% to >99% ee).

Chiral-Anion-Mediated Asymmetric Heck-Matsuda Reaction of Acyclic Alkenyl Alcohols.

Acyclic internal alkenes are a class of challenging substrates in asymmetric Heck-type reactions due to difficulties related to both reactivity and selectivity control. Employing acyclic alkenyl alcohols, an asymmetric Heck-Matsuda reaction is developed through the strategy of chiral anion phase transfer. Various chiral ketones could be obtained in high levels of enantioselectivity. A catalytic amount of dimethyl sulfoxide (DMSO) as an additive is crucial for the reaction to suppress the palladium-hydride-mediated side reactions.

Potential for Ladderane (Bio)synthesis from Oligo-Cyclopropane Precursors.

Quantum chemical calculations were used to determine the energetic viability of several mechanisms for formation of ladderanes from oligocyclopropanes. Pathways involving radical cations, diradicals, and carbocations were considered, and a hybrid of carbocation and radical cation pathways was predicted to have the lowest overall barrier.

Effects of supplying silicon nutrient on utilization rate of nitrogen and phosphorus nutrients by rice and its soil ecological mechanism in a hybrid rice double-cropping system.

This study was conducted to reveal the effects of silicon (Si) application on nutrient utilization efficiency by rice and on soil nutrient availability and soil microorganisms in a hybrid rice double-cropping planting system. A series of field experiments were conducted during 2017 and 2018. The results showed that Si nutrient supply improved grain yield and the utilization rates of nitrogen (N) and phosphorus (P) to an appropriate level for both early and late plantings, reaching a maximum at 23.4 kg/ha Si. The same trends were found for the ratios of available N (AN) to total N (TN) and available P (AP) to total P (TP), the soil microbial biomass carbon (MBC), microbial biomass nitrogen (MBN), microbial biomass phosphorus (MBP), and the ratios of MBN to TN and MBP to TP, at different levels of Si. Statistical analysis further revealed that Si application enhanced rice growth and increased the utilization rate of fertilizer due to an ecological mechanism, i.e., Si supply significantly increased the total amount of soil microorganisms in paddy soil compared to the control. This promoted the mineralization of soil nutrients and improved the availability and reserves of easily mineralized organic nutrients.

[Impact of Newly Build Lead-Acid Battery Agglomeration Area on the Surrounding Soil Environment: A Study Based on the Spatial Characteristics of Heavy Metals].

To determine whether the newly built lead-acid battery agglomeration area in a town in northern Zhejiang had an impact on the surrounding soil environment after seven years of operation, 76 samples of surface soil around the lead-acid battery concentration area were collected, and the contents of Hg, As, Cu, Zn, Pb, Cd, Ni, and Cr in the soil were determined. Based on the spatial distance of the agglomeration area and 50, 450, and 850 m from the agglomeration area boundary, the soil environmental quality was evaluated using the single factor index, Nemerow comprehensive pollution index, and potential ecological risk index methods. The spatial distribution characteristics of the heavy metals were analyzed using the geostatistical method, and the sources of heavy metals affecting the soil environment were determined by correlation analysis. The results showed that the average contents of Hg, Zn, and Pb in eight heavy metals were higher than their corresponding background values at all spatial scales. The average Cd content in spatial scales other than the agglomeration area was larger than its background value. Only As at 50 m was greater than its background value, whereas the average content of other elements at all spatial distances was lower than their corresponding background values. The spatial variability was high for Hg and Cd but not obvious for other elements. This implies that the influence of regional activities was concentrated mainly on Hg and Cd; the content of both increased with distance from the agglomeration area. Hg and Cd exceeded the risk screening values and were distributed mainly at 450 m and 850 m; 33.33% and 38.89% Hg points and 27.78% and 55.56% Cd points were observed at these distances, respectively. The spatial distribution characteristics of Hg and Cd were consistent with their contents; only Zn and Pb had scattered points that exceeded the risk screening values and generally no obvious spatial distribution characteristics. According to the risk analysis of soil comprehensive pollution caused by the eight heavy metals, Cd was the main source of soil comprehensive pollution risk at a contribution rate of 36.73%, which caused the soil at 850 m to be in a state of alert. Soil ecological risk at a medium level occurred mainly at 450 m and 850 m outside the agglomeration area from Hg and Cd. The contribution rates to the soil quality at these distances were 46.30% and 39.37% for Hg and 38.98% and 49.30% for Cd, respectively. This indicates that regional activities caused Hg and Cd to be the main elements affecting soil quality in the study area. The results of geostatistics and multivariate statistical analysis showed that Hg and Cd were diffused inward from the periphery of the agglomeration area on the axis of the local main wind direction (northeast-southwest), and the main sources of both were coal-burning activities of enterprises in the periphery of the agglomeration area. In summary, the newly build lead-acid battery agglomeration area has not significantly affected the accumulation of heavy metals in the agglomeration area and in the surrounding soil after seven years of operation.

Palladium-catalyzed enantioselective carboannulation of 1,3-dienes with aryl iodides enables access to chiral indanes.

A palladium-catalyzed enantioselective carboannulation of 1,3-dienes and aryl iodides has been established by using a BINOL-based phosphoramidite ligand. This reaction proceeded via a tandem Heck-type insertion and asymmetric intramolecular Tsuji-Trost allylic alkylation, providing indane derivatives with high levels of enantioselectivity (up to >99% ee).

An Asymmetric Dehydrogenative Diels-Alder Reaction for the Synthesis of Chiral Tetrahydrocarbazole Derivatives.

An asymmetric dehydrogenative Diels-Alder reaction of 2-methyl-3-phenylmethylindoles and α,ß-unsaturated aldehydes has been established. The successful in situ generation of the indole ortho-quinodimethane intermediate and the iminium activation of enals are the keys to success, providing various tetrahydrocarbazole derivatives with up to >99% ee.

Pd(II)-Catalyzed Asymmetric Oxidative 1,2-Diamination of Conjugated Dienes with Ureas.

A palladium(II)-catalyzed asymmetric 1,2-diamination of 1,3-dienes with readily available dialkylureas was established by using a chiral pyridine-oxazoline ligand. The diamination reaction exclusively occurs at the terminal C-C double bond of the 1,3-dienes to give 4-vinylimidazolidin-2-ones in high yields and with excellent levels of enantioselectivity (up to 99% yield, 97% ee). The reaction could feasibly be applied for gram-scale synthesis with a 1:1 ratio of the diene and the urea.

[Optical spectral verification of a harmful impurity to palladium catalyst].

The condensation of glyoxal with benzylamine leaded to hexabenzyl-hexaazaisowurtzitane (HBIW) with formic acid catalyst, and at the same time some side products were produced. Some impurities in HBIW would be harmful to the palladium catalyst used in the hydrogenolysis of HBIW, subsequently resulting in the low yield or failure of the catalytic reaction. The impurities in hexabenzylhexaazaisowurtzitane were distilled by means of recrystal technic, which were isolated by preparative chromatograph. The structure of the main impurity was studied with FTIR, 1H-NMR, ESI-MS, and element analysis. The result shows that the structure is comfirmed as N,N'-dibenzyl-oxalamide. which was synthesized in the way reported in the literature, and was charactered by FTIR, 1H-NMR and EI-MS. And the optical spectra data of the sample synthesized and the substance isolated from the impuries were the same, testifying that the substance isolated was N, N'-dibenzyl-oxalamide ulteriorly. N, N'-dibenzyl-oxalamide was added in the hydrogenolysis system of HBIW catalyzed by Pd catalyst. The result shows that N, N'-dibenzyl-oxalamide can reduce the activity of Pd catalyst, and when the quantity of N,N'-dibenzyl oxalmine added achievs 0.9% of the weight of HBIW, the reaction of catalytic hydrogenolysis fails.