Studies on the Development for New Synthetic Reagents of Organic Sulfur and Selenium Compounds and their Organization

1.研究发现，苯基3-和4-吡啶亚砜通过格氏交换反应生成3-和4-吡啶基溴化镁，再与各种醛、酮反应生成相应的加成产物。通过这种交换反应，合成了光学活性的3-和4-吡啶基苯亚砜。另一方面，2-吡啶基苯亚砜在类似的条件下得到高产率的配体偶联产物，即2-吡啶基衍生物。2-Pys(O)Ph与LDA(二异丙胺锂)反应，得到高区域选择性的3-锂化亚砜，再与亲电试剂反应生成3-取代的2-苯基亚硫基吡啶。在格氏试剂作用下，这些吡啶衍生物最终得到了光学活性的2-苯基吡啶。采用上述方法首次合成了具有光学活性的2-对甲苯基吡啶亚砜。光学纯的2-PYCH_2S(O)-Tol-p在LDA和ArCHO作用下，不对称诱导生成α-苯基烷氧基取代亚砜。脱氢反应后，合成了光学活性的1-芳基-2-(2-吡啶)乙醇。在LDA和(PHS)_2等亲电试剂的作用下，4，6-二取代硫和硒的氧化物被转化为4，6-二取代的衍生物。此外，4，6-二取代的硫和硒的1-氧化物与n-BuLito反应生成缩合的1，9-二取代的二苯并噻吩环和二苯并硒环。这些1，9-二取代二苯并噻吩类和二苯并硒类化合物在热解和光解反应中提供了[3.4，BC][3.4，BC]噻吩类和硒类化合物。

1.It was found that phenyl 3- and 4-pyridyl sulfoxides underwent Grignard exchange reactions to afford readily 3-and 4-pyridyl magnesium bromide which reacted with various aldehydes and ketones to give the corresponding addition products. By using this exchange reactions, optically active 3-and 4-pyridylphenyl sulfoxides were prepared. On the other hand, 2-pyridyl phenyl sulfoxide gave under similar condition to provide the ligand coupling products.i.e., 2-pyridyl derivatives in high yields. The reaction of 2-PyS(O) Ph with LDA (lithium diisopropylamide) gave highly regioselectively the 3-lithiated sulfoxide which then reacts with electrophiles to result in the formation of the 3-substituted 2-phenylsulfinyl pyridines. These pyridyl derivatives gave finally optically active 2-phenyl pyridines on treatment with Grignard reagents. Also first synthesis of optically active 2-p-tolyl pyridyl sulfoxide was performed by employing the above mentioned procedure.2. On treatment with LDA and then with ArCHO,optically pure 2-PyCH_2S(O)-Tol-p gave a-phenyl alkoxyl substituted sulfoxides by asymmetric induction. After desulfinylation, optically active 1-aryl-2-(2-pyridyl)ethanols were synthesized.3. Monooxides of thianthrene and selenanthrene were converted to 4,6-disubstituted derivatives by treatment with LDA and electrophiles such as (PhS)_2. Furthermore,4,6-disubstituted thianthrene and selenanthrene 1-oxides were found to react with n-BuLito give the ring contracted 1,9-disubstituted dibenzothiophenes and dibenzoselenophenes. These 1,9-disubstituted dibenzothiophenes and dibenzoselenophenes provide [3.4, bc]thienothiophene and selenophene on pyrolysis and photolysis.