The synthesis, structure, and reactivity of organoyttrium phosphides toward phenyl isocyanate (PhNCO) isothiocyanate (PhNCS) are described. Reaction (TpMe2)CpYCH2Ph(THF) (TpMe2 = tris(3,5-dimethylpyrazolyl)borate; Cp C5H5) with 1 equiv HPPh2 in THF at ambient temperature gives an phosphide (TpMe2)CpYPPh2(THF) (1). Treatment PhNCO results monoinsertion into the Y–P σ-bond to yield complex (TpMe2)CpY[OC(PPh2)NPh](THF) (2), whereas reaction 2 affords diinsertion product...

The structurally characterized Tp(Me2)-supported rare earth metal monoalkyl complex (Tp(Me2))CpYCH(2)Ph(THF) (1) was synthesized via the salt-metathesis reaction of (Tp(Me2))CpYCl(THF) with KCH(2)Ph in THF at room temperature. Treatment 1 equiv PhC≡CH under same conditions afforded corresponding alkynyl (Tp(Me2))CpYC≡CPh(THF) (2). Complex exhibits high activity toward carbodiimides, isocyanate, isothiocyanate, and CS(2); treatment such substrates led to formation a series Y-C(benzyl) σ-bond...

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 simple and efficient synthetic approach is reported for the synthesis of highly functionalized 4‐amino‐iminocoumarins 4 4‐aminoquinolines 6 in moderate to excellent yields, through a copper‐catalyzed multicomponent reaction. The reaction carried out one‐pot manner, using readily available terminal alkynes 1 , sulfonyl azides 2 2‐hydroxybenzonitriles 3 or 2‐aminobenzonitrile ( 5 ) as substrates at slightly elevated temperature under N . protocol operationally has good substrate scope....

Currently, most conventional methods to achieve imidazo[1,5-a]pyridines have limitations for the synthesis of 3-acyl imidazo[1,5-a]pyridines. Herein, a novel and efficient Cu(I)-catalyzed three-component annulation method valuable by reaction 2-pyridinyl-substituted p-QMs, terminal alkynes, TsN3 in presence O2 under mild conditions successfully been developed. The investigation indicated that molecular oxygen (O2) TsN3, respectively, serving as nitrogen sources, were essential successful...

TpMe2LnCl2 (1) reacts with 2 equiv of KN(SiMe3)2 in tetrahydrofuran at room temperature to yield the ligand redistribution/γ-deprotonation products [(TpMe2)2Ln]+[((Me3Si)2N)2Ln(CH2)SiMe2N(SiMe3)]− [Ln = Er (2), Y (3)]. Complex can also be obtained by reacting [(Me3Si)2N]2ErCl KTpMe2. However, 1 1.5 and [(TpMe2)2Er]+[((Me3Si)2N)3ErCl]− (4) [(TpMe2)2Er]+{[(Me3Si)2N)TpMe2ErCl]2(μ-Cl)2K}− (5), respectively. Furthermore, it is found that CyN═C═NCy (Cy cyclohexyl) give tandem HN(SiMe3)2...

The mixed TpMe2/Cp-supported yttrium monoalkyl (TpMe2)CpYCH2Ph(THF) (1) reacted with 1 equiv of PhCN in THF at room temperature to afford the imine–enamine tautomer (TpMe2)CpY(N(H)C(Ph)═CHPh)(THF) (2) and insertion product (TpMe2)CpY(N═C(CH2Ph)Ph)(THF) (3), 61% 12% isolated yields, respectively. 2 further toluene 120 °C give N–H bond addition (TpMe2)CpY(N(H)C(Ph)NC(Ph)═CHPh) (4). Treatment anthranilonitrile produced dimer [(TpMe2)CpY(μ-NHC6H4CN)]2 (5). monomer (TpMe2)CpY(NHC6H4CN)(HMPA) (6)...

A novel Tp(Me2)-supported (Tp(Me2) = tri(3,5-dimethylpyrazolyl)borate) rare earth metal complex promoted Me-Si cleavage of the bis(trimethylsilyl) amide ligand ([(Me(3)Si)(2)N](-)) was observed. Reaction Tp(Me2)LnCl(2) with 2 equiv K[(RN)(2)CN(SiMe(3))(2)] (KGua) gave methylamidinate complexes Tp(Me2)Ln[(RN)(2)CMe][N(SiMe(3))(2)] (R isopropyl, Ln Y (1(Y)), Er (1(Er)); R cyclohexyl, (2(Y))) in moderate yields. In contrast, Tp(Me2)YCl(2)(THF) reacted 1 KGua to afford a C-N product...

The TpMe2-supported yttrium dialkyl TpMe2Y(CH2Ph)2(THF) (TpMe2 = tri(3,5-dimethylpyrazolyl)borate) reacted with 1 equiv of ArNH2 in THF at room temperature to afford the alkyl primary amido complexes TpMe2YNHAr(CH2Ph)(THF) (Ar Ph (1), C6H3-iPr2-2,6 (2)) 84% and 88% isolated yields, respectively. Complex iPrN═C═NiPr give a dianionic guanidinate complex, TpMe2Y[(iPrN)2C═NPh](THF)2 (3, 74%). However, reaction ArN═C═NAr C6H3-iPr2-2,6) same conditions produced Y–C bond insertion product,...

A "new" strategy for the preparation of organolanthanide neutral hydrides by reaction chlorides with metallic potassium and their reactivity toward isocyanide has been studied. Treatment [Me2Si(C5H4)2LnCl]2 excess in THF results a direct chlorine-abstracted to yield corresponding {μ-[η5-Me2Si(C5H4)2Ln]}2(μ-H)2 (Ln = Y (1), Er (2), Gd (3)) moderate yields. Structural determination indicated that complex 1 is solvated dimer two bridging hydrogen atoms. Further investigations on display...

The dissociation of the anionic guanidinate ligand NC(NMe2)2 promoted by rare-earth metal complexes at room temperature is described. Treatment CpLnCl2(THF)3 with two equiv. Li[NC(NMe2)2] in THF affords [Cp2Ln(μ-η1:η2-L2)]2 (Ln = Y; L NC(NMe2)NC(NMe2)2) and CpLn[NC(NMe2)2](μ-η1:η2-L)2LnCp2 Dy) moderated yields, respectively. YCl3 reacts three under same conditions to give a trinuclear yttrium [(Me2N)2CN]5Y3[μ-NC(NMe2)2]2(μ-η1:η2-L)2 63% yield. These reactions show that metals can promote C–N...

Abstract Unusual chemical transformations such as three‐component combination and ring‐opening of N‐heterocycles or formation a carbon–carbon double bond through multiple C–H activation were observed in the reactions Tp Me2 ‐supported yttrium alkyl complexes with aromatic N‐heterocycles. The scorpionate‐anchored dialkyl complex [Tp Y(CH 2 Ph) (THF)] reacted 1‐methylimidazole 1:2 molar ratio to give rare hexanuclear 24‐membered rare‐earth metallomacrocyclic compound Y( μ ‐ N , C ‐Im)(η ‐Im)]...

Abstract A facile, one‐step, direct functionalization of the C1 and N positions tetrahydroisoquinolines was developed. Unprotected tetrahydroisoquinolines, indoles, benzaldehydes could be used as starting materials. The different substituted indoles were investigated in detail scope proved to broad.

Abstract A copper‐catalyzed one‐pot approach to α‐aryl amidines from terminal alkynes, sulfonyl azides, and aryl sulfonamides via a Truce‐Smiles rearrangement under mild condition in good excellent yields was reported for the first time. The formation of such aryl‐ sp 3 C−C bond previously could not be directly achieved by common method. stoichiometry substrates played an important role improving desired products. In addition, two sets signals were observed 1 H NMR spectra their possible...

The products containing pyrimidine scaffolds exhibit various important physiological and biological activities. To date, the strategies to generate 4,5,6-trisubstituted pyrimidines were not reported. Here, a copper-catalyzed reaction of 2H-azirines with α-isocyanoacetates or α-isocyanoacetamides has been developed, rapidly preparing pyrimidines. mechanistic results reveal that this strategy underwent formal 1, 3-dipolar [3 + 2] cycloaddition/ring-expanding/oxidative aromatization procedure...

We report a formal [3 + 2] cycloaddition for constructing 3-aryl pyrido[1,2- ]indoles from aryne intermediates and 2-pyridinyl-substituted p -QMs under ambient conditions.

A terminal alkyne-assisted protocol for the one-pot formation of a diverse range arylamidines from novel cascade reaction in situ generated nitrile oxides, sulfonyl azides, alkynes, and water by [3 + 2] cycloaddition ring opening sequence was developed. The use aryl oxime chlorides as carbon source amidine group addition proved to be critical reaction. Moreover, which can lead high yields products employing less amount, may play catalytic role broader substrates investigated.

Abstract Conventional methods for the general and efficient synthesis of 4‐hydroxybenzo‐ phenones are extremely underdeveloped limited. We herein report a challenging metal‐free protocol to rapidly construct 4‐hydroxybenzophenones from para ‐quinone methides ( p ‐QMs) in DMSO presence KOH using inexpensive readily available elemental sulfur as redox reagent. As an unprecedented method, this simple but approach has excellent site specificity, green sustainability, atomic economy, broad...

A new, step-economical and operationally simple access to unsubstituted 1,2-dihydroisoquinolin-3(4<italic>H</italic>)-imines by Cu-catalyzed MCRs under mild conditions is described.

A facile transition-metal-free protocol to form 2-iminoimidazo[1, 2-a]-pyridines bearing a -CHBr2 group and an aza-quaternary carbon center at the 3 position from N-(2-pyridyl)amidines substrates, in which new heterocyclic skeletons constructed amidines via radical reactions or nucleophilic substitution are promoted only by CBr4 under mild conditions, is demonstrated. The were realized intramolecular CDC reaction involving C-N C-C bond formation sequential C(sp3)-H bifunctionalization mode...

Fuchsones have wide applications in modern society. Present methods for generating fuchsones many disadvantages and there are significant limitations further exploration of fuchsone applications. Herein, we describe a DMSO-promoted direct δ-selective arylation p-QMs to synthesize symmetrical unsymmetrical under metal-free conditions by employing themselves or substituted phenols as aryl sources. As unprecedented methods, these novel strategies present great advantage significance the development new

An efficient synthesis of prasugrel, a thienopyridine ADP-receptor antagonists, is described. A inter-mediate was prepared by N-protection, boric acid substitution and N-substitution. After hydrolysis the methyl ether subsequent acetylation, prasugrel obtained with total yield 50% after seven linear steps from 4,5,6,7-tetrahydrothieno [3,2-c]pyridine 2-bromo-1-cyclopropyl-2-(2- fluorophenyl)ethan-1-one as raw materials.

Abstract A facile approach to a rare class of 3,3‐disubstituted 2‐iminoimidazo[1,2‐ ]‐pyridines bearing hydroxyl group at the 3 position in good excellent yields from N ‐(2‐pyridyl)amidines substrates presence CuI/I 2 /KI/KO t Bu is described. According investigation, use Cu catalyst and sulfonyl groups has remarkable influence on success oxidative cyclization reaction. Moreover, oxygen source may be incorporation water reaction system or KO Bu. The successful implementation further...