【作者】 赵玉军；

【导师】 周永贵；

【作者基本信息】 中国科学院研究生院（大连化学物理研究所） ， 有机化学， 2005， 硕士

【摘要】 本论文包括两部分,一部分为二茂铁衍生的手性硫膦配体的合成及在喹啉不对称氢化中的应用,同时研究了平面手性的作用;另一部分为酒石酸衍生的手性配体的合成。一.二茂铁衍生的手性硫膦配体的合成及在喹啉不对称氢化中的应用从原料(S)-1出发合成了二茂铁衍生的手性硫膦配体3a-3f。为了研究茂环上取代基的空间效应,在配体3的茂环上引入TMS基团而合成了配体5。为了研究平面手性对产物的ee值和绝对构型的影响,从相同的原料(S)-1出发,合成了具有相同的中心手性和相反的平面手性的配体7和8。二茂铁衍生的手性硫膦配体在喹啉的不对称氢化反应中显示较好的活性和中等到良好的对映选择性。平面手性在反应中的作用也被研究,(S)-型中心手性和(R)-型平面手性是匹配的。在具有相同中心手性和相反平面手性的配体的茂环上引入大体积的TMS得到的配体5和7,可以得到相反绝对构型的产物。二.酒石酸衍生的手性配体的合成从易得的酒石酸出发,根据已知的方法,可以方便的合成手性二醇关键中间体16。通过羟基甲磺酰氯保护,叠氮化钠取代和氢化铝锂还原可以合成手性二胺,用对甲苯磺酰氯单保护或双保护,能分别得到配体20a和20b。中间体16衍生为环状硫酸酯,然后用叠氮化钠开环,还原得到氨基醇23,用对甲苯磺酰氯保护氨基得到手性配体24。更多还原

【Abstract】 Chiral S,P-ligands derived from ferrocene were synthesized. The application of these chiral ligands in asymmetric hydrogenation of quinolines was carried out, and the role of planar chirality was also examined.i) Synthesis of chiral S,P-ligands derived from ferrocene and application in asymmetric hydrogenation of quinolinesUsing commercially available (S)-1 as the starting material, the chiral S,P- ferrocenyl ligands 3a-3f were synthesized according to the known method. To study the effect of steric hinderance in Cp ring on activity and enantioselectivity, ligand 5 with TMS group in Cp ring of ligand (S,Rp)-3 was synthesized. To explore the role of planar chirality on the enantioselectivity and absolute configuration of the products, ligands 7, 8 with same central chirality and reversal planar chirality were also synthesized from the same starting material (S)-1.Iridium complexes with S,P-ligands showed good activity and enantioselectivity for asymmetric hydrogenation of quinolines. The planar chirality played an important role in the reaction, (S)-central chirality and (Rp)-planar chirality is matched. When a bulky TMS group was introduced to Cp ring, two ligands 5,7 with the same central chirality and reversal planar chirality gave the desirable products with high enantioselectivities and reversal absolute configurations. Furthermore, both enantiomers of 1,2,3,4-tetrahydroquinoline derivatives were obtained using the same chiral starting material derived two更多还原