Nickel/Photoredox-Catalyzed Asymmetric Reductive Cross-Coupling of Racemic α-Chloro Esters with Aryl Iodides

A unique nickel/organic photoredox co-catalyzed asymmetric reductive cross-coupling between α-chloro esters and aryl iodides is developed. This cross-electrophile coupling reaction employs an organic reductant (Hantzsch ester), whereas most reductive cross-coupling reactions use stoichiometric metals. A diverse array of valuable α-aryl esters is formed under these conditions with high enantioselectivities (up to 94 %) and good yields (up to 88 %). α-Aryl esters represent an important family of nonsteroidal anti-inflammatory drugs. This novel synergistic strategy expands the scope of Ni-catalyzed reductive asymmetric cross-coupling reactions.     

Conjugate addition of pyrroles to α,β-unsaturated ketones using copper bromide as a catalyst

Copper bromide was used as a catalyst for the addition of pyrroles to enones. When both the reactants were used in equimolar amounts, mono and dialkylated products were obtained. However, the use of excess enone furnished only dialkylated products. Thus, copper bromide was shown to be an efficient catalyst for the dialkylation of pyrroles.     

A novel synthesis of 5-perfluorophenyl 4,5-dihydro-1H-pyrazoles in THF or water

5-Perfluorophenyl 4,5-dihydro-1H-pyrazoles were synthesized from 1,3-dipolar cycloaddition reaction of perfluorobenyl 2,4,6-triisopropylbenzenesulfonylhydrazone and α,β-unsaturated carbonyl compounds or acrylonitrile in THF or water. It was worthy to note that better results were obtained when water was employed as the solvent, which was considered as an effective, economic and environmentally friendly method to synthesize these pyrazole derivatives.     

Microwave-accelerated conjugate addition of aldehydes to α,β-unsaturated ketones

Aldehydes undergo smooth conjugate addition to α,β-unsaturated ketones in the presence of 5-(2-hydroxyethyl)-1,3-thiazolium halides and DBU adsorbed onto the surface of basic alumina under microwave irradiation and solvent-free conditions to afford 1,4-diketones in enhanced yields and reduced reaction times compared to conventional methods.     

New stereoselective synthesis of the peptidic aminopeptidase inhibitors bestatin, phebestin and probestin

Peptidic aminopeptidase inhibitors, bestatin, phebestin and probestin have been prepared by stereo- and regiocontrolled reactions from a common α,β-epoxy ester precursor.     

Palladium catalyzed mild reduction of α,β-unsaturated compounds by triethylsilane

The palladium(II) chloride/triethylsilane system has been successfully applied for the selective hydrogenation of the carbon-carbon double bond of α,β-unsaturated ketones to yield the corresponding saturated carbonyl compounds. The reaction takes place under mild conditions and affords high yields.     

Novel approach to arylhydrazones, the precursor for Fischer indole synthesis, via diazo esters derived from α-amino acid esters

A novel method for synthesizing arylhydrazones, the precursor for Fischer indole synthesis, using aryllithium reagents and α-diazo esters that are easily obtained from α-amino acid esters, is described.     

An unusual 1,2-N→C acyl migration in urea derivatives of α-aminoorganolithiums

Transmetalation of urea derivatives of α-aminoorganostannanes with alkyllithiums provides α-aminoorganolithiums which undergo rapid N to C acyl migration to afford α-aminocarboxamides. The stereochemical course of the transmetalation/migration process depends on the substituents on the urea and varies from complete retention of configuration to complete racemization.     

Asymmetric synthesis of 6-(2′,3′,4′,5′,6′-pentafluorophenyl)-δ-lactones via “allyl”boranes: application for the synthesis of fluorinated analog of key pharmacophore of statin drugs

Asymmetric “allyl”boration of pentafluorobenzaldehyde with various α-pinene based “allyl”boranes provides homoallylic alcohols in high de and ee; the alcohols have been converted into δ-lactones via acryloylation, ring-closing metathesis and hydrogenation. Pentafluorophenyl analog of key pharmacophore of statin drugs has been synthesized using diastereoselective epoxidation and regioselective reduction as key steps.     

基于Karhunen-Loève变换和小波谱特征矢量量化的三维谱像数据压缩

提出了基于Karhunen Lo埁ｖｅ变换的小波谱特征矢量量化三维谱像数据压缩方法耍幔颍瑁酰睿澹?Lo埁ｖｅ变换 /小波变换 /小波谱特征矢量量化方法应用了Karhunen Lo埁ｖｅ变换的消除谱相关性优良性能 ,应用二维小波变换消除空间相关性 ,在小波变换域内应用二维集分割嵌入块编码和一维谱特征矢量量化对三维谱像数据压缩 ,获得较高的压缩性能。实验结果表明 :Karhunen Lo埁ｖｅ变换 /小波变换 /小波谱特征矢量量化编码比Karhunen Lo埁ｖｅ变换 /小波变换 /改进对块零树编码和Karhunen Lo埁ｖｅ变换 /小波变换 /快速矢量量化编码方法在同样压缩比条件下 ,峰值信噪比提高 2dB和 1dB以上 ,而速度提高了 1.5和 8倍 ,整体压缩性能有较大的提高