Homocoupling of aldimines mediated by zirconocene: synthesis of vicinal diamines and imidazolidines

The reductive coupling of imines in the presence of the lanthanide-originated zirconocene equivalent allows the synthesis of vicinal diamines or imidazolidines under mild conditions in good yields with high diastereoselectivity.     

Innovative reactions mediated by zirconocene

Radical reactions mediated by Schwartz reagent and zirconocene(alkene) complex are firstly described. Schwartz reagent is a promising alternative to tributyltin hydride and the first transition metal hydrido complex used as a radical mediator in organic synthesis. A zirconocene(alkene) complex effects single electron transfer to alkyl halide to generate the corresponding alkyl radical. Secondly, serendipitous allylic C-H bond activation of the coordinating alkene of zirconocene(alkene) complex and its application to organic synthesis are summarized. By utilizing equilibrium between zirconocene(alkene) and zirconocene 2-alkenyl hydride, reaction of acid chloride with zirconocene(alkene) provides the corresponding homoallylic alcohol by sequential attacks of the hydride and 2-alkenyl moieties. A set of hydride and 2-alkenyl attacks on 1,4-diketone yields 6-heptene-1,4-diol derivative in high yield with high stereoselectivity. Selective capture of the hydride with diisopropyl ketone gives zirconocene 2-alkenyl alkoxide, which is a useful reagent for stereoselective allylation of aldehyde and imine. alpha-Halo carbonyl compounds undergo radical allylation with the zirconocene 2-alkenyl alkoxide which serves as a substitute for allyltin.     

Titanocene and zirconocene σ-alkynyl complexes in C---C single bond coupling and cleavage reactions

Group 4 metallocene mono- and bis-σ-alkynyl complexes of the type L₂M(σ-CCR) and L₂M(σ-CCR)₂ with M=titanium and zirconium in the oxidation states +3 and +4 and L=Cp (η⁵-cyclopentadienyl) and Cp^* (η⁵-pentamethylcyclopentadienyl) are important compounds for stoichiometric and catalytic C---C single bond coupling and cleavage reactions. Detailed investigations show five-membered metallacyclocumulenes L₂M(η⁴-1,2,3,4-RC₄R) as the key intermediates in both reactions of a C---C single bond cleavage of different 1,4-substituted 1,3-butadiynes RCC---CCR to alkynyl groups and the opposite reaction of C---C single bond formation starting from alkynyl groups under the formation of 1,4-substituted 1,3-butadiynes. Depending on different metals M and ligands L, coupling or cleavage is favoured. Combination of both reactions offered the first C---C single bond metathesis in homogeneous solution, which is photocatalyzed and titanocene-mediated. It proceeds via titanocene–mono-alkynyl complexes, which are interesting species also for other stoichiometric and catalytic C---C coupling reactions. Some similarities regarding the σ-to-π conversion exist between the coupling of the alkynyl groups at titano- and zirconocenes to complexed 1,3-butadiynes on one side and the coupling of phenyl groups at chromium to complexed diphenyl on the other side.     

Highly efficient transition metal-free coupling of acid chlorides with terminal alkynes in [bmim]Br: A rapid route to access ynones using MgCl2

A simple, mild, highly efficient and transition metal-free protocol for synthesis of ynones in an ionic liquid is described. In this approach, the coupling reaction of different acid chlorides with terminal alkynes was efficiently carried out using 0.05 mol% MgCl₂ in the presence of triethylamine in [bmim]Br at room temperature to afford the corresponding ynones in good to excellent yields. This method is highly efficient for various acid chlorides and alkynes including aliphatic, aromatic, and heteroaromatic substrates bearing different functional groups. The influence of some parameters in this reaction including type of ionic liquid, base and catalyst has been discussed.     

Catalytic coupling of terminal alkynes with isonitriles promoted by organoactinide complexes

The coupling reaction of terminal alkynes and tert-butylisonitrile to yield substituted alpha,beta-acetylenic aldimines is catalyzed by the organoactinide neutral complexes Cp*2AnMe2 (Cp* = C5Me5, An = Th, U) and the cationic complex [(Et2N)3U][BPh4]. The reaction proceeds by a 1,1-insertion of the isonitrile into the metal-acetylide bond. Additional insertion products can be obtained by altering the catalyst and the reactant ratios. A plausible mechanism for the catalytic reaction is presented, in addition to the crystal structure of Cp*2UMe2     

新的炔烃聚合催化体系及其聚合物性质的研究

报导由「（ＣＯ）５ＭｏＣ（Ｏ）Ｒ」．Ｎ（ＣＨ３）４＋Ｅｇ３ＯＢＦ４＋ＡｌＣｌ３（无水）组成炔烃聚合催化体系。通过研究该体系对二苯乙炔的催化聚合，讨论聚合尖条件对聚合物得率的影响和聚合反应机理。     

Chalcogenide-Lewis acid mediated reactions of electron-deficient alkynes with aldehydes

Reactions of but-3-yn-2-one (2) with aldehydes 1 in the presence of a Lewis acid and dimethyl sulfide (3 a) predominantly gave (E)-alpha-(halomethylene)aldols 4-5 in high yields, while reactions of methyl propiolate (6 a) mainly afforded (Z)-3-halogeno-2-(hydroxymethyl)acrylates 7-8 in low to moderate yields. A reaction of dimethyl acetylenedicarboxylate (10) with 1 a in the presence of TiCl(4) and 1,1,3,3-tetramethylthiourea (3 c) produced maleate (E)-11 (40 %) and butenolide 12 (40 %). When a reaction of 6 a with 1 a was carried out in the presence of TiBr(4) and 3 a (0.2 equiv) at -20 degrees C for 60 h, 3-(methylthio)-2-(hydroxyalkyl)acrylate 9 a was obtained in an 8 % yield. Experiments were conducted in order to elucidate the formation mechanism of 9 a, and it was made clear that 9 a was formed via the processes of the Michael addition of sulfide 3 a to alkynoate 6 a and an aldol reaction with 1 a and demethylation.     

Facile synthesis of fluorinated α-imino alkynes by the coupling reaction of imidoyl iodides with terminal alkynes

A series of N-arylbromodifluoroacetimidoyl iodides and 1-alkynes were converted into α-imino alkynes by using Pd(Ph₃)₂Cl₂/CuI as the catalyst under mild conditions. The reaction proceeded smoothly to give the coupling products in good to excellent yields.     

Synthesis of 5-functionalized-1,2,3-triazoles via a one-pot aerobic oxidative coupling reaction of alkynes and azides

In this paper, an efficient synthesis of 5-alkynyl-1,2,3-triazoles through a one-pot aerobic oxidative coupling reaction of various alkynes and azides has been developed. Further derivatization of 5-alkynyl-1,2,3-triazoles readily yielded 5-carbonyl-1,2,3-triazoles, 5-carboxylic-1,2,3-triazole, 5-hydroxyalkyl-1,2,3-triazoles and 5-quinoxaline-1,2,3-triazole, which provided an entry into structurally diverse 5-functionalized-1,2,3-triazoles.     

Suzuki and Heck coupling reactions mediated by palladium complexes bearing trans-spanning diphosphines

Palladium complexes of three trans-spanning diphosphines are examined for effecting C-C coupling reactions. Ten aryl halides of varying electron density were screened in Suzuki coupling reactions with phenylboronic acid and in Heck reactions with styrene. The results are discussed in terms of the unique flexibility and shape of the meta-terphenyl backbone upon which the diphosphine ligand is built.     

Arylcyanation of alkynes catalyzed by nickel

A nickel catalyst prepared from Ni(cod)₂ and PMe₃ is found to effect arylcyanation reaction of alkynes, namely, cleavage of a C-CN bond of an aryl cyanide followed by addition of each fragment across an alkyne. A wide range of functional groups in aryl cyanides tolerated the catalysis, giving variously functionalized β-arylalkenenitriles stereoselectively.     

催化动力学光度法测定痕量锆（Ⅳ）

研究了在稀盐酸介质中，α，α’－联吡啶存在下，锆催化溴酸钾氧化考马斯亮蓝Ｇ使其褪色这一新的指示反应及其动力学条件，建立了灵敏地测定痕量锆的新方法。该方法检出限为８．９８×１０＾－１１ｇ／ｍＬ，线性范围０－１０．４μｇ／Ｌ，用于合金钢中痕量锆的测定，结果满意．     

Synthesis of indoles via palladium-catalyzed C-H activation of N-aryl amides followed by coupling with alkynes

A convenient and efficient method for the construction of indole skeleton was developed via Pd-catalyzed C-H activation of N-aryl amides and subsequent coupling with alkynes. Both stoichiometric and catalytic versions have been successfully achieved.     

Bis(enamino-Cp) Group 4 metal complex chemistry: developing a Mannich-type carbon-carbon coupling reaction at the bent metallocene famework

Treatment of 6-methyl-6-dimethylaminofulvene (2a) with methyl lithium in ether results in a deprotonation reaction to yield the enamino-substituted lithium cyclopentadienide reagent 3a. Its reaction with zirconium tetrachloride (0.5 molar equivalents) results in the formation of the [1-dimethylaminobutadien-1,3-diyl-bis(cyclopentadienyl)]zirconium dichloride product 4a. The unsaturated ansa-metallocene is probably formed via a Lewis acid-catalyzed Mannich-type carbon-carbon coupling reaction of an in situ generated bis[(dimethylaminoethenyl)cyclopentadienyl]ZrCl₂ intermediate. A number of related examples of this condensation reaction at the intact Group 4 bent metallocene framework is described, using different amino-substituents and Ti, Zr and Hf systems. Three examples of the unsaturated ansa-metallocene systems were characterized by X-ray diffraction. In a few cases it was possible to isolate the open (enamino-Cp)₂ZrCl₂ complexes. In the case of, e.g., (piperidinoethenylcyclopentadienyl)₂ZrCl₂ (13c) treatment with a catalytic quantity of the Lewis acid ZrCl₄ or the Brønsted acid resulted in a clean conversion to the respective Mannich condensation product, here the ansa-metallocene complex 4c. The strongly electrophilic borane HB(C₆F₅)₂ did not catalyze the CC-coupling reaction under the applied reaction conditions but added cleanly to the enamino-CC double bond of, e.g., 13c to yield a cyclic nitrogen donor-stabilized hydroboration product (19).     

Hydrocarboxylation of unactivated internal alkynes with carboxylic acids catalyzed by dinuclear palladium complexes

Dinuclear palladium complexes catalyzed addition reactions of carboxylic acid O-H bond to unactivated internal alkynes. The reaction afforded a trans-adduct selectively.     

催化反应-示波极谱法测定痕量钒

在硫酸介质及100℃水浴加热条件下,钒(Ⅴ)对过硫酸铵氧化二苯羟乙酸生成二苯甲酮这一慢反应具有强烈的催化作用,据此拟定了一个测定8.0～100ng/ml钒的催化反应-示波极谱法,并用于测定铝合金及纯铝中钒的含量。     

Selective annulation of benzamides with internal alkynes catalyzed by an electron-deficient rhodium catalyst

An electron-deficient [Cp^ERhCl₂]₂ catalyzed annulation of N-pentafluorophenylbenzamides with internal alkynes was successfully established under mild reaction conditions, with the assistance of Lewis acid silver salt. Particularly, electron-deficient benzamide substrates were smoothly transformed into the desired products in this catalytic system. The catalytic system showed a broad tolerance for different substituents on the aromatic rings or aryl, alkyl-substituted alkynes.     

Hydrosilylation of alkynes catalyzed by ruthenium carbene complexes

Hydrosilylation of terminal alkynes with a variety of silanes catalyzed by Cl₂(PCy₃)₂RuCHPh (1) affords mainly the Z-isomer via trans addition in excellent yields. The presence of a hydroxyl group in close proximity to the triple bond was observed to exert a strong directing effect, resulting in the highly selective formation of the α-isomer. Intramolecular hydrosilylation of a homopropargylic silyl ether was demonstrated to give the cis addition product.