Homoleptic octahedral Co complexes as precatalysts for regioselective hydroboration of alkenes with high turnover frequencies.

Homoleptic complexes adopting octahedral coordination modes are usually less active in catalysis due to the saturated coordination around metal centers that prevents substrate activation in a catalytic event. In this work, we demonstrated that a homoleptic octahedral cobalt complex (1) of 4'-pyridyl-2,2';6',2''-terpyridine that experienced monoprotonation at the non-coordinating pyridyl moiety upon crystallization could serve as a highly efficient precatalyst for the hydroboration of styrene derivatives with Markovnikov selectivity. The solid-state structure of this precatalyst along with relevant homoleptic Co and Fe complexes has been characterized by X-ray crystallography.

Vanadium-catalysed regioselective hydroboration of epoxides for synthesis of secondary alcohols.

Regioselective epoxide ring-opening through hydroboration catalysed by a vanadium(III) dialkyl complex supported by a redox-active terpyridine ligand is reported. Secondary alcohols were obtained in high yields effective Markovnikov hydroboration of terminal epoxides, showcasing a new catalytic application of an earth-abundant vanadium(III) complex.

A clinical prediction model for lung metastasis risk in osteosarcoma: A multicenter retrospective study.

Background: Lung metastases (LM) have a poor prognosis of osteosarcoma. This study aimed to predict the risk of LM using the nomogram in patients with osteosarcoma.

Methods: A total of 1100 patients who were diagnosed as osteosarcoma between 2010 and 2019 in the Surveillance, Epidemiology and End Results (SEER) database were selected as the training cohort.

An ionic Fe-based metal-organic-framework with 4'-pyridyl-2,2':6',2''-terpyridine for catalytic hydroboration of alkynes.

An ionic metal-organic-framework (MOF) containing nanoscale channels was readily assembled from ditopic 4'-pyridyl-2,2':6',2''-terpyridine (pytpy) and a simple iron(ii) salt. X-ray structural analysis revealed a two-dimensional grid-like framework assembled by classic octahedral (pytpy)Fe cations as linkers (with pytpy as a new ditopic pyridyl ligand) and octa-coordinate FeCl centers as nodes. The layer-by-layer assembly of the 2-D framework resulted in the formation of 3-D porous materials consisting of nano-scale channels.

Markovnikov alcohols via epoxide hydroboration by molecular alkali metal catalysts.

Synthesis of branched "Markovnikov" alcohols is crucial to various chemical industries. The catalytic reduction of substituted epoxides under mild conditions is a highly attractive method for preparing such alcohols. Classical methods based on heterogeneous or homogeneous transition metal-catalyzed hydrogenation, hydroboration, or hydrosilylation usually suffer from poor selectivity, reverse regioselectivity, limited functional group compatibility, high cost, and/or low availability of the catalysts.

Diplumbane-catalysed solvent- and additive-free hydroboration of ketones and aldehydes.

A new diplumbane, namely [Pb(CHSiMe)], was synthesized and structurally characterized. This group 14 element compound was found to catalyse the hydroboration of ketones and aldehydes under mild conditions without the use of additives and solvents, leading to the synthesis of a range of alcohols in high yields after hydrolysis.

One-Pot Synthesis of 1-Hydroxyacridones from -Quinols and -Methoxycarbonylaryl Isocyanates.

A variety of substituted acridones were synthesized via a one-pot, metal-free cascade reaction. In this event, the DBU-mediated addition between quinols and -methoxycarbonylaryl isocyanates formed a bicyclic oxazolidinone, followed by a sequence of intramolecular condensation, tautomerization, and decarboxylation, which led to the formation of acridones. The acridones showed mild activity against the human cytomegalovirus.

1-D manganese(ii)-terpyridine coordination polymers as precatalysts for hydrofunctionalisation of carbonyl compounds.

Reductive catalysis with earth-abundant metals is currently of increasing importance and shows potential in replacing precious metal catalysis. In this work, we revealed catalytic hydroboration and hydrosilylation of ketones and aldehydes achieved by a structurally defined manganese(ii) coordination polymer (CP) as a precatalyst under mild conditions. The manganese-catalysed methodology can be applied to a range of functionalized aldehydes and ketones with turnover numbers (TON) of up to 990.

Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C═X (X = O, N) Functionalities.

Catalysis is the second largest application for V after its use as an additive to improve steel production. Molecular complexes of vanadium(V) are particularly useful and efficient catalysts for oxidation processes; however, their ability to catalyze reductive transformations has yet to be fully explored. Here we report the first examples of polar organic functionality reduction mediated by V.

Copper(II)-Catalyzed Selective Hydroboration of Ketones and Aldehydes.

A novel nonanuclear copper(II) complex obtained by a facile one-pot self-assembly was found to catalyze the hydroboration of ketones and aldehydes with the absence of an activator under mild, solvent-free conditions. The catalyst is air- and moisture-stable, displaying high efficiency (1980 h turnover frequency, TOF) and chemoselectivity on aldehydes over ketones and ketones over imines. This represents a rare example of divalent copper catalyst for the hydroboration of carbonyls.

Markovnikov-Selective Hydroboration of Vinylarenes Catalyzed by a Cobalt(II) Coordination Polymer.

Highly efficient and practical hydroboration of alkenes has been catalyzed by an inexpensive and air-stable cobalt(II) coordination polymer (CP) in the presence of KO Bu. Complete conversion of alkenes to alkylboronates were performed within just 5 min with low catalyst loading (0.025 mol %), achieving the record high turnover frequencies of up to 47 520 h.

Cobalt(II) Coordination Polymer as a Precatalyst for Selective Hydroboration of Aldehydes, Ketones, and Imines.

Highly effective hydroboration precatalyst is developed based on a cobalt(II)-terpyridine coordination polymer (CP). The hydroboration of ketones, aldehydes, and imines with pinacolborane (HBpin) has been achieved using the recyclable CP catalyst in the presence of an air-stable activator. A wide range of substrates containing polar C═O or C═N bonds have been hydroborated selectively in excellent yields under ambient conditions.

Cobalt-Catalyzed α-Alkylation of Ketones with Primary Alcohols.

An ionic cobalt-PNP complex is developed for the efficient α-alkylation of ketones with primary alcohols for the first time. A broad range of ketone and alcohol substrates were employed, leading to the isolation of alkylated ketones with yields up to 98%. The method was successfully applied to the greener synthesis of quinoline derivatives while using 2-aminobenzyl alcohol as an alkylating reagent.

The Effect of Cage Shape on Nanoparticle-Based Drug Carriers: Anticancer Drug Release and Efficacy via Receptor Blockade Using Dextran-Coated Iron Oxide Nanocages.

Although a range of nanoparticles have been developed as drug delivery systems in cancer therapeutics, this approach faces several important challenges concerning nanocarrier circulation, clearance, and penetration. The impact of reducing nanoparticle size on penetration through leaky blood vessels around tumor microenvironments via enhanced permeability and retention (EPR) effect has been extensively examined. Recent research has also investigated the effect of nanoparticle shape on circulation and target binding affinity.

Highly Selective Hydroboration of Alkenes, Ketones and Aldehydes Catalyzed by a Well-Defined Manganese Complex.

Well-defined manganese complexes based on inexpensive, readily available ligands, 2,2':6',2''-terpyridine and its derivatives have been prepared and employed for the selective hydroboration of alkenes, ketones and aldehydes. Highly Markovnikov regioselective hydroboration of styrenes as well as excellent chemoselective hydroboration of ketones over alkenes were achieved, for the first time, by an earth-abundant manganese catalyst.

Cobalt-Catalyzed N-Alkylation of Amines with Alcohols.

A well-defined nonprecious metal cobalt(II) catalyst based on a pincer PNP ligand has been employed for the efficient N-alkylation of both aromatic and aliphatic amines with alcohols. A subtle change of reaction conditions (simply adding 4 Å molecular sieves) was observed to readily switch the resulting products (amines vs imines) with high chemoselectivity. A range of alcohols and amines including both aromatic and aliphatic substrates were efficiently converted to secondary amines in good-to-excellent yields when 2 mol % cobalt catalyst was used.

Synthesis of o-chlorophenols via an unexpected nucleophilic chlorination of quinone monoketals mediated by N,N'-dimethylhydrazine dihydrochloride.

An unexpected nucleophilic chlorination of a quinone monoketal while carrying out a pyrazolidine synthesis has led to a general preparation of multisubstituted phenols. The products are obtained in good to high yields under mild conditions. The bridged pyrazolidines that were the original targets are obtained in the presence of a protic solvent.

Double hetero-Michael addition of N-substituted hydroxylamines to quinone monoketals: synthesis of bridged isoxazolidines.

A general synthesis of bridged isoxazolidines from a double hetero-Michael addition of N-substituted hydroxylamines to quinone monoketals has been developed. The different addition order of N-benzylhydroxylamine and N-Boc hydroxylamine is also discussed. Moreover, the various functionalities in the isoxazolidine products allow facile derivatization.

Bioactive and marker compounds from two edible dark-colored Myrciaria fruits and the synthesis of jaboticabin.

Jaboticaba (Myrciaria cauliflora) and false jaboticaba (Myrciaria vexator) fruits are two pleasant-tasting, dark-colored fruits, native to Brazil. They are rich sources of phenolic compounds, including anthocyanins, flavonoids, phenolic acids, and tannins, as well as less well known polyphenols such as depsides. These two fruits are very similar in morphology, but their taste profiles differ markedly.

An expedient stereoselective and chemoselective synthesis of bicyclic oxazolidinones from quinols and isocyanates.

A mild and efficient synthesis of bicyclic oxazolidinones from quinols and isocyanates, under DBU-mediated conditions at room temperature, is described. The aza-Michael addition to substituted cyclohexadienones is stereoselective and chemoselective.

Synthesis and catalytic properties of diverse chiral polyamines.

Chiral polyamines can be utilized for a variety of potential applications, ranging from asymmetric catalysis to nonviral gene delivery systems for DNA and RNA. They can also be utilized to solubilize carbon nanotubes. Thus, methods for the straightforward synthesis of chiral polyamines are needed.