Facile synthesis of chiral 2-formyl-1,1′-binaphthyl via lipase-catalyzed acylation and hydrolysis of 1,1′-binaphthyl oximes

Lipase-catalyzed acylation of 2-hydroxyiminomethyl-1,1′-binaphthyl [(±)-1] and hydrolysis of 2-acetoxyiminomethyl-1,1′-binaphthyl [(±)-2] yielded optically active oximes 1 and 2 with high enantiomeric excess. Successful synthesis of the optically active aldehyde 4 from chiral O-acetyl oxime 2 occurred without a decrease of enantiomeric excess.     

N-糖基硫代亚脲基—(硫代)磷酰胺二芳基和二烷基酯的合成

二芳氧基磷酰肼(2a，2b)或二乙氧基硫代磷酰肼(4)与糖基异硫氰酸酯(5a-5b) 反应，生成相应的N-糖基硫代亚脲基—磷酰胺二芳基酯(6a-6d,7a-7d)和N-糖基硫 代亚脲基—硫代磷酰胺二乙基酯(8a-8d)．     

SYNTHESIS OF CHIRAL BINAPHTHYL CROWN ETHERS AND THEIR USE IN ANIONIC POLYMERIZATION OF METHYL METHACRYLATE AS INITIATOR LIGANDS

INTRODUCTIONAnionic polymerization of MMA could be carried out with alkyllithium or Grignard reagent etc. in a non-polarsolvent. However, this polymerization system often involves multiple active species and side reactions dependingon initiator, countercation, solvent and polymerization temperature etc. Therefore, the molecular weightdistribution and stereomicrostructure of PMMA obtained would be very different[1-4]. These differences wouldbe mainly caused by the nucleophilic attack of…     

Synthesis and chirooptical properties of optically active poly(ester imide)s based on axially asymmetric 1,1′‐binaphthyls

A series of optically active poly(ester imide)s (PEsI's) has been synthesized by the polycondensation reactions of new axially asymmetric dianhydrides, that is, (R)‐2,2′‐bis(3,4‐dicarboxybenzoyloxy)‐1,1′‐binaphthyl dianhydride and (S)‐2,2′‐bis(3,4‐dicarboxybenzoyloxy)‐1,1′‐binaphthyl dianhydride, and various diamines with aromatic, semiaromatic, and aliphatic structures. The polymers have inherent viscosities of 0.45–0.70 dL/g, very good solubility in common organic solvents, glass‐transition temperatures of 124–290 °C, and good thermal stability. Wide‐angle X‐ray crystallography of these polymers shows no crystal diffraction. In comparison with model compounds, an enhanced optical rotatory power has been observed for the repeat unit of optically active PEsI's based on aromatic diamines, and it has been attributed to a collaborative asymmetric perturbation of chiral 1,1′‐binaphthyls along the rigid backbones. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4318–4326, 2004     

Phase Transfer Catalyzed Synthesis of 1,6-Diaroyldithiohydrazodicarbonamide Derivatives

Reaction of hydrazine hydrate with aroyl chloride and ammonium thiocyanate under the condition of solid-liquid phase transfer catalysis using polyethylene glycol-600 (PEG-600) as the catalyst yielded 1, 6-diaroyldithiohydrazodicarbonamides 3a—3h in good to excellent yield.     

含1,1′-联萘基团可溶性聚酯酰亚胺的合成与性质

从１ ,１′联２ ,２′萘酚出发合成了新型具有非共平面结构的联萘类二酐单体,即２ ,２′（３ ,３′,４ ,４′四酸二酐） 二苯甲酰氧基１ ,１′联萘． 通过联萘二酐与不同二胺单体的溶液缩聚反应制备得到了一系列新型聚酯酰亚胺． 聚合物表现出良好的溶解性、热性能及薄膜透光性．     

Synthesis of triaryls: hydroxy and amine dinaphthyl and diphenanthryl aryls by one-pot electron-transfer nucleophilic substitution reactions

A new one-pot synthetic route to achieve the preparation of hydroxy and amine binaphthyl and biphenanthryl aryls is here reported. This approach involves the reaction of 1,4-bromoiodobenzene, 4,4′-diiodobiphenyl, and 1,4- and 1,5-diiodonaphthalene with the anions of 2-naphthylamine, 2-naphthol, and 9-phenanthrylamine under irradiation in liquid ammonia. The reactions proceed to afford triaryl derivatives in moderate to good yields (∼45% of 1,4-phenylene- and 1,4-naphthylene-1,1′-dinaphthalen-2-ols as well as 1,4-phenylene-1,1′-dinaphthalen-2-amine and 10,10′-diphenanthren-9-amine). Lower yields (27%) of polyaryl derivatives are obtained by reaction of 4,4′-diiodobiphenyl with anions of 2-naphthol and 9-phenanthrylamine.     

Synthesis and Chiral Separation of Dinucleotide（TpAZT） Phosphoramidates

Dinucleotide (TpAZT) phosphoramidates were synthesized by Todd reaction of dinucleoside H-phosphonates and amino acid methyl esters, and their diastereomers (Rp and Sp) were separated by crystallization, and the results showed that natural and cheap methyl esters of alanine and phenylalanine can be used for large-scale synthesis of dinucleotide analogs.