基于C-H官能团化策略构建平面手性与轴手性分子的研究
发布时间：2018-08-25 19:00
【摘要】：本论文主要研究基于 C-H官能团化策略构建平面手性与轴手性分子。主要包括如下三章内容:通过钯催化的3-芳基-1-(2-碘苄基)-1H-吲哚的分子内环化构建轴手性分子,BF3·OEt2诱导的茂金属烯酮的分子内环化构建环已酮并茂金属以及过渡金属官能团化2,3:6,7-二苯并二环[3.3.1]辛烷-2,6-二烯-4,8-二酮,并合成新型V-型分子。第一章:利用改造的TADDOL亚膦酰胺配体采用C-H官能团化策略实现了 3-芳基-1-(2-碘苄基)-1H-吲哚的分子内不对称环化反应。可以以最高产率99%,最高对映选择性91%ee得到吲哚-芳基轴手性化合物,该反应条件温和,官能团兼容性较好。进一步对产物的氧化和水解我们可以得到新型的轴手性分子骨架。第二章:利用BF3·OEt2诱导茂金属烯酮经过重排环化过程构建了茂金属并环已酮结构。该反应没有经历正常的Nazarov环化生成茂金属并环戊酮,而是生成了茂金属并环已酮结构,我们猜测反应可能是经历一个1,2-H迁移接着发生分子内傅-克烷基化环化的过程。在研究产物酮的α位烷基化时还发现了亲电试剂优先从位阻较大的第二个Cp环同方向进攻。第三章:基于手性二酮的骨架利用C-H官能团化策略合成了具有平面手性的Pd,Ir金属的络合物,所合成的金属络合物的结构可以通过核磁以及单晶得以确认。此外初步研究了所得的金属络合物在催化氢化还原以及1,2加成反应中的应用。最后在NBS和Pd(OAc)2的作用下我们实现了对手性二酮的双溴代反应,进而合成了新型的手性V-型结构的分子。
[Abstract]:In this thesis, planar chiral and axial chiral molecules were constructed based on C-H functionalization strategy. The main contents are as follows: the intramolecular cyclization of 3-aryl-1- (2-iodobenzyl) -1H-indoles catalyzed by palladium to form cyclohexanone and metallocene and transition metal induced by chiral molecule BF3 OEt2. Functional group formation 2: 3: 6: 7-dibenzobicyclic [3.3.1] octane-2o-6-diene-4-diketone, A novel V-type molecule was synthesized. Chapter 1: the intramolecular asymmetric cyclization of 3-aryl -1- (2-iodobenzyl) -1H-indole was achieved by using the modified TADDOL ligands with C-H functionalization strategy. The chiral compounds of indole aryl axis can be obtained with the highest enantioselectivity of 91 and the highest yield of 99. The reaction conditions are mild and the functional group compatibility is good. A novel axial chiral molecular skeleton can be obtained by further oxidation and hydrolysis of the product. Chapter 2: Metallocene and cyclohexanone structures were constructed by BF3 OEt2 induced cyclization of metallocene enones. This reaction did not undergo normal Nazarov cyclization to form metallocene and cyclopentanone, but formed metallocene and cyclohexanone structure. We speculate that the reaction may undergo a 1 ~ 2-H migration followed by intramolecular Friedel-keto-alkylation cyclization. The 伪 -site alkylation of ketones was also studied. It was also found that the electrophilic reagents were preferentially attacked from the second Cp ring with larger steric resistance in the same direction. Chapter 3: based on the framework of chiral diketone, the complex of planar chiral Pd,Ir metal is synthesized by C-H functionalization strategy. The structure of the synthesized metal complex can be confirmed by nuclear magnetic field (NMR) and single crystal. In addition, the application of the metal complexes in catalytic hydrogenation reduction and 1H 2 addition reaction was studied. Finally, we have realized the dibromination of chiral diketones under the action of NBS and Pd (OAc) _ 2, and then we have synthesized novel chiral V-type molecules.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4;O621.251
本文编号：2203809
[Abstract]:In this thesis, planar chiral and axial chiral molecules were constructed based on C-H functionalization strategy. The main contents are as follows: the intramolecular cyclization of 3-aryl-1- (2-iodobenzyl) -1H-indoles catalyzed by palladium to form cyclohexanone and metallocene and transition metal induced by chiral molecule BF3 OEt2. Functional group formation 2: 3: 6: 7-dibenzobicyclic [3.3.1] octane-2o-6-diene-4-diketone, A novel V-type molecule was synthesized. Chapter 1: the intramolecular asymmetric cyclization of 3-aryl -1- (2-iodobenzyl) -1H-indole was achieved by using the modified TADDOL ligands with C-H functionalization strategy. The chiral compounds of indole aryl axis can be obtained with the highest enantioselectivity of 91 and the highest yield of 99. The reaction conditions are mild and the functional group compatibility is good. A novel axial chiral molecular skeleton can be obtained by further oxidation and hydrolysis of the product. Chapter 2: Metallocene and cyclohexanone structures were constructed by BF3 OEt2 induced cyclization of metallocene enones. This reaction did not undergo normal Nazarov cyclization to form metallocene and cyclopentanone, but formed metallocene and cyclohexanone structure. We speculate that the reaction may undergo a 1 ~ 2-H migration followed by intramolecular Friedel-keto-alkylation cyclization. The 伪 -site alkylation of ketones was also studied. It was also found that the electrophilic reagents were preferentially attacked from the second Cp ring with larger steric resistance in the same direction. Chapter 3: based on the framework of chiral diketone, the complex of planar chiral Pd,Ir metal is synthesized by C-H functionalization strategy. The structure of the synthesized metal complex can be confirmed by nuclear magnetic field (NMR) and single crystal. In addition, the application of the metal complexes in catalytic hydrogenation reduction and 1H 2 addition reaction was studied. Finally, we have realized the dibromination of chiral diketones under the action of NBS and Pd (OAc) _ 2, and then we have synthesized novel chiral V-type molecules.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4;O621.251
【参考文献】
相关期刊论文 前1条
1 张松;陆俊筑;叶金星;段伟良;;手性磷酸控制的不对称碳氢芳基化反应合成平面手性二茂铁化合物[J];有机化学;2016年04期
，本文编号：2203809
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