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

1.结果表明，3-和4-吡啶基苯基亚砜通过格氏交换反应可以得到3-和4-吡啶基溴化镁，并与各种醛和酮反应生成相应的加成产物。利用该交换反应制备了具有光学活性的3-和4-吡啶苯基亚砜。另一方面，2-吡啶基苯基亚砜在类似条件下给出配体偶联产物，即。2-吡啶基衍生物的高收率。2-PyS(O) Ph与LDA（二异丙酰胺锂）反应得到高度区域选择性的3-锂化亚砜，然后与亲电试剂反应生成3-取代的2-苯基亚砜基吡啶。这些吡啶基衍生物经格氏试剂处理后，最终得到旋光活性的2-苯基吡啶。采用上述方法首次合成了具有旋光性的2-对苄基吡啶亚砜。先用LDA处理，再用ArCHO处理，光纯的2-PyCH_2S(O)- tolp通过不对称诱导得到了a-苯基烷氧基取代亚砜。经脱硫后，合成了具有光学活性的1-芳基-2-（2-吡啶基）乙醇。噻吩和硒蒽的单氧化物经LDA和（phs_2）等亲电试剂处理后转化为4,6-二取代衍生物。此外，还发现4,6-二取代噻吩和硒- 1-氧化物与n-BuLito反应生成了环状收缩的1,9-二取代二苯并噻吩和二苯并噻吩。这些1,9-二取代的二苯并噻吩和二苯并硒苯在热解和光解作用下产生[3.4，bc]噻吩和硒苯。

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.