The first example of rare earth metal-catalyzed cycloaddition terminal alkynes to azides resulting in the formation 1,5-disubstituted 1,2,3-triazoles is described. Preliminary studies revealed that present shows unprecedented mechanistic features involving a tandem anionic cascade cyclization and anti-addition across CC triple bond.

Homoleptic lanthanide complex Y[N(TMS)2]3 is an efficient homogeneous catalyst for the hydroboration reduction of secondary amides and tertiary to corresponding amines. A series containing different functional groups such as cyano, nitro, vinyl were found be well-tolerated. This transformation has also been nicely applied synthesis indoles piribedil. Detailed isotopic labeling experiments, control kinetic studies provided cumulative evidence elucidate reaction mechanism.

We have developed a lanthanide/B(C6F5)3-promoted hydroboration reduction of indoles and quinolines with pinacolborane (HBpin). This reaction provides streamlined access to range nitrogen-containing compounds in moderate excellent yields. Large-scale synthesis further transformations bioactive indicate that the method has potential practical applications. Preliminary mechanistic studies suggest amine additives promote formation indole-borane intermediates, proceeds via intermediates HBpin...

Lanthanide-catalyzed alkynyl exchange through C-C single-bond cleavage assisted by a secondary amino group is reported. A lanthanide amido complex proposed as key intermediate, which undergoes unprecedented reversible β-alkynyl elimination followed and imine reinsertion. The in situ homo- cross-dimerization of the liberated alkyne can serve an additional driving force to shift metathesis equilibrium completion. This reaction formally complementary conventional allows selective transformation...

The rare-earth-metal organic cyclo-P4 complex (LY·DMAP)2[1,2-R2-cyclo-P4] (2, L = N,N′-2,6-diisopropylphenyl-1,4-diazabutadiene, DMAP 4-N,N′-dimethylpyridine, R CH2C6H4NMe2-2) was synthesized by direct functionalization of P4 using the alkyl LYR(THF) (1) for first time. Further investigations indicated that three selective conversions species have been realized migration. Complex 2 slowly transformed into a R2P-substituted cyclo-P3 cluster (LY·DMAP)2[cyclo-P3PR2] (3) under heating...

Lithium-promoted hydroboration of alkynes and alkenes using commercially available hexamethyldisilazane lithium as a precatalyst HBpin hydride source has been developed. This method will be appealing for organic synthesis because its remarkable substrate tolerance good yields. Mechanistic studies revealed that the proceeds through in situ-formed BH3 species, which acts to drive turnover alkenes.

The instability of curcumin's structure and the toxic side effects piperlongumine have limited their potential applications in cancer treatment. To overcome these challenges, we designed synthesized a novel curcumin-piperlongumine hybrid molecule, 3-[(

Abstract Bacterial infections are closely correlated with the genesis and progression of cancer, elimination cancer‐related bacteria may improve efficacy cancer treatment. However, combinatorial therapy that utilizes two or more chemodrugs will increase potential adverse effects. Image‐guided photodynamic is a highly precise to treat tumor microbial infections. Herein, four donor–acceptor–π‐bridge–acceptor (D–A–π–A) featured near‐infrared (NIR) aggregation‐induced emission luminogens...

This report describes the LuCl

Abstract A series of unusual chemical‐bond transformations were observed in the reactions high active yttriumdialkyl complexes with unsaturated small molecules. The reaction scorpionate‐anchored yttriumdibenzyl complex [Tp Me2 Y(CH 2 Ph) (thf)] ( 1 , Tp =tri(3,5‐dimethylpyrazolyl)borate) phenyl isothiocyanate led to CS bond cleavage give a cubane‐type yttrium–sulfur cluster, {Tp Y(μ 3 ‐S)} 4 ), accompanied by elimination PhNC(CH . However, compound reacted isocyanate afford C(sp )H...

A high-efficiency and atom-economic route for the synthesis of N-aryl-substituted propiolamidines was established through addition terminal alkynes with aryl-substituted symmetrical or unsymmetrical carbodiimides catalyzed by mixed TpMe2/Cp rare-earth-metal alkyl complexes (TpMe2)CpLnCH2Ph(THF) (1Ln). Moreover, gadolinium complex 1Gd can also serve as a catalyst double dialkynes carbodiimides. Mechanism studies indicated that variable coordination modes (κ3 κ2) TpMe2 ligand on species may...

A facile boron induced electron-withdrawing/donating strategy is demonstrated to regulate the electronic configuration of Fe–N 4 sites in Fe–N–C catalysts optimize absorption/desorption oxygen intermediates during reduction reaction.

Commercially available and inexpensive lithium tert-butoxide ( t BuOLi) acts as a good precatalyst for the hydroboration of esters, lactones, epoxides using pinacolborane borylation agent. Functional groups such cyano-, nitro-, amino-, vinyl, alkynyl are unaffected under presented process, representing high chemoselectivity. This transformation has also been effectively applied to synthesis key intermediates Erlotinib Cinacalcet. Preliminary investigations mechanism show that proceeds...

The homoleptic lanthanide complex Sm[N(TMS)₂]₃ is an efficient rare-earth catalyst for the hydroboration of alkynes to corresponding alkenylboron compounds.

The reactions of β-diketiminatoyttrium dialkyl complex LY(CH2Ph)2(THF) (1, L = [{N(2,6-iPr2C6H3)C(Me)}2CH]−) with a series aromatic N-heterocycles such as 2-phenylpyridine, benzothiazole, and benzoxazole were studied displayed discrete reactivity including C–H activation, C–C coupling, ring-opening/insertion, dearomatization. reaction 1 2-phenylpyridine in 1:2 molar ratio THF at 30 °C for 14 days afforded structurally characterized metal complex, LY(η2-N,C-C5H4NC6H4-2)[C5H4N(CH2Ph-4)Ph] (2),...

Treatment of the yttrium dialkyl complex TpMe2Y(CH2Ph)2(THF) (TpMe2 = tri(3,5 dimethylpyrazolyl)borate, THF tetrahydrofuran) with S8 in a 1:1 molar ratio at room temperature afforded pentasulfide TpMe2Y(κ4-S5) (THF) (1) 93% yield. The monoalkyl TpMe2CpYCH2Ph(THF) reacted 1:0.5 under same conditions to give another [(TpMe2)2Y]+[Cp2Y(κ4-S5)]− (10) low Further investigations indicated that S52– anion facilely turned into corresponding thioethers or organic disulfides, and released redundant S8,...

Abstract We report herein a rare‐earth‐metal‐catalyzed insertion of 2‐pyridine C( sp 2 )−H bond into an intramolecular unactivated vinyl bond. This reaction provides streamlined access to range azaindolines in moderate excellent yields. The salient features this include simple and mild conditions, 100% atom efficiency, wide substrate scope. methodology is also used construct other nitrogen‐containing compounds such as naphthyridine derivatives. A plausible mechanism for the formation...

The rare-earth/lithium cooperative effect on functionalization of white phosphorus has been investigated. reaction diazabutadiene-supported yttrium hydride chelated a LiPPh2 molecule (LY ⋅ THF)2 (μ-H)2 [μ-PPh2 (Li)] (1, L=N,N'-di(2,6-diisopropylphenyl)-1,4-diazabutadiene) with P4 gave two novel mixed Y/Li multinuclear polyphosphorus complexes [cyclo-P3 ]Li(THF)3 (2) and [Li(THF)4 ]+ [(LY THF)3 (norborane-P7 )Li(THF)]- (3), accompanied the elimination diphosphorus compound Ph2 PPPh2 (4) H2 ....

Cobalt-catalyzed borylative reduction of azobenzenes using pinacolborane is developed. The simple cobalt chloride catalyst and reaction conditions make this protocol attractive for hydrazobenzene synthesis. This shows good functional group compatibility can be readily scaled up to the gram scale. Preliminary mechanistic studies clarified proton source hydrazine products. cobalt-catalyzed azobenzene provides a practical prepare synthetically useful diborylated hydrazines.

The three-component tandem reaction of 2-aminobenzonitriles, arylboronic acids and ketones as available reagents allowing the synthesis polysubstitution quinolines is reported.

A practical, convenient, and highly selective method of synthesizing β-ketonitriles from the Pd-catalyzed addition organoboron reagents to dinitriles has been developed. This provides excellent functional-group tolerance, a broad scope substrates, convenience using commercially available substrates. The is expected show further utility in future synthetic procedures.

A new method for converting easy availability starting materials 2-(2-oxoindolin-3-yl)acetonitrile, arylboronic acids, and alcohols into 2-arylquinoline-4-carboxylates is reported. The procedure involves a three-component addition/ring expansion/esterification reaction in the presence of Pd(II) catalyst with high functional group tolerance under mild conditions. In addition, photophysical properties resulting product were investigated exhibited excellent polarity-sensitive fluorescence AIE property.