氯化铜催化偶联合成4-烷基联苯

4-烷基联苯是重要的液晶中间体. 以氯化铜为C—C键偶联反应催化剂, 经过对溴联苯的Grignard试剂直接与溴代烷烃发生偶联反应, 成功合成了一系列4-烷基联苯类化合物, 部分化合物产率高达91%左右, 并对其反应条件进行了初步研究; 所合成化合物结构都经过元素分析、红外光谱、核磁共振氢谱和质谱鉴定. 与现有方法相比, 此合成方法收率高、环境友好、成本相对较低.     

Convenient Method for the Reduction of the Double-Bond of Cyclic Vinylphosphine Oxides Using Borane

The electronpoor double-bond of cyclic vinylphosphine oxides (1, 3 and 4) is easily reduced by borane in a selective manner to give the corresponding saturated derivatives (2, 4 and 5, respectively) Under forcing conditions, change of the functionality may also take place.     

Nickel‐Catalyzed Cross‐Electrophile Coupling with Organic Reductants in Non‐Amide Solvents

Cross‐electrophile coupling of aryl halides with alkyl halides has thus far been primarily conducted with stoichiometric metallic reductants in amide solvents. This report demonstrates that the use of tetrakis(dimethylamino)ethylene (TDAE) as an organic reductant enables the use of non‐amide solvents, such as acetonitrile or propylene oxide, for the coupling of benzyl chlorides and alkyl iodides with aryl halides. Furthermore, these conditions work for several electron‐poor heterocycles that are easily reduced by manganese. Finally, we demonstrate that TDAE addition can be used as a control element to ‘hold’ a reaction without diminishing yield or catalyst activity.     

Triphenylphosphine‐Mediated Deoxygenative Reduction of CF3SO2Na and Its Application for Trifluoromethylthiolation of Aryl Iodides

We report herein a practical method for taming Langlois’ reagent CF₃SO₂Na to generate CuSCF₃ by a triphenylphospine‐mediated deoxygenative reduction process. This chemistry highlights a novel utilization of the inherent CF₃S skeleton of Langlois’ reagent as a CF₃S feedstock under mild conditions. The CuSCF₃ intermediate generated by this protocol can react with a wide array of supporting ligands to furnish several air‐stable [LCu(SCF₃)] complexes as valuable trifluoromethylthiolating agents. In addition, the CuSCF₃ intermediate can be directly employed for the trifluoromethylthiolation of (hetero)aryl iodides with operational simplicity and atomic efficiency.     

Synthesis of lipophilic bisanthracene fluorophores: versatile building blocks toward the synthesis of new light-harvesting dendrimers

Lipophilic bisanthracene-based fluorophore and its derivatives were synthesized by the Suzuki-Miyaura cross-coupling reaction of 9-anthrylboronic acid with a substituted dibromobenzene. In addition to desirable fluorescent properties, these molecular systems were demonstrated to serve as versatile building blocks toward the synthesis of two types of new light-harvesting dendrimers due to their chemical stability.     

Bis(triphenylphosphine)palladium(II)succinimide as a precatalyst for Suzuki cross-coupling—subtle effects exerted by the succinimide ligand

A new palladium(II) precatalyst for Suzuki cross-coupling of aryl halides and organoboronic acids has been identified, namely bis(triphenylphosphine)palladium(II)succinimide [(Ph₃P)₂Pd(N-Succ)₂] 2. The precatalyst is easily prepared from palladium(0) precursors, such as (Ph₃P)₄Pd or Pd₂dba₃·CHCl₃/Ph₃P and succinimide, is air, light and moisture stable, and may be employed with a variety of substrates to give the cross-coupled products, in good yields and in reasonable time, at relatively low catalyst loadings.     

A new approach to the synthesis of racemic analogs of 1,5-dimethyl-branched insect pheromones from 4-methyltetrahydropyran

A new procedure was developed for the synthesis of racemic analogs of 1,5-dimethyl-branched insect pheromones based on monoalkylation of ethyl acetoacetate with 1-acetoxy-5-bromo-3-methylpentane produced upon decyclization of 4-methyltetrahydropyran.     

Synthesis and Pd-catalyzed coupling of1-C-stannylated glycals

Abstract

1-Tributylstannyl glycals were applied as versatile tools in the Pd(0)-mediated synthesis of glycal phthalonitrile conjugates. Likewise, selective homo-coupling of 1-tributylstannyl glycals furnishing C1-C1’ linked glycal dimers was investigated by using Pd(II)-species. For both Stille type couplings the rate-accelerating effect of copper(I) thiophene-2-carboxylate (CuTC) was exploited. The synthesis of stannylated glycal precursors was significantly improved by establishing a one-pot two-step procedure via glycosyl sulfoxides.     

Lactam Coupling as a Versatile Route to Indoprofen Analogs

A convergent synthesis of indoprofen via a Buchwald coupling approach is reported. Using this methodology, indoprofen and a set of analogs of indoprofen were readily prepared.     

Synthesis, structure determination, and (radio-)fluorination of novel functionalized phosphanes suitable for the traceless Staudinger ligation

An elegant and efficient synthesis approach for the preparation of novel benzoate and nicotinate containing phosphanes is presented. This reaction path has a broad substrate scope. Thus, various functionalized phosphanes were obtained in high yields using an esterification procedure under Steglich conditions. A facile blocking of the phosphorus atom with BH₃ was carried out. BH₃ as easily insertable and removable protecting group enables a further derivatization of the benzoate residue. The prepared phosphane derivatives proved to be valuable labeling building blocks for the implementation of a bioorthogonal (radio-)fluorination strategy and were applied for labeling purposes using the traceless Staudinger ligation. For this purpose, a selection of azide-functionalized small organic and bioactive sample molecules was prepared. Furthermore, a mild and selective (radio-)fluorination of these derivatives is demonstrated adopting this bioorthogonal ligation method.