基于C-H官能團化策略構(gòu)建平面手性與軸手性分子的研究
發(fā)布時間：2018-08-25 19:00
【摘要】：本論文主要研究基于 C-H官能團化策略構(gòu)建平面手性與軸手性分子。主要包括如下三章內(nèi)容:通過鈀催化的3-芳基-1-(2-碘芐基)-1H-吲哚的分子內(nèi)環(huán)化構(gòu)建軸手性分子,BF3·OEt2誘導(dǎo)的茂金屬烯酮的分子內(nèi)環(huán)化構(gòu)建環(huán)已酮并茂金屬以及過渡金屬官能團化2,3:6,7-二苯并二環(huán)[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亞膦酰胺配體采用C-H官能團化策略實現(xiàn)了 3-芳基-1-(2-碘芐基)-1H-吲哚的分子內(nèi)不對稱環(huán)化反應(yīng)�？梢砸宰罡弋a(chǎn)率99%,最高對映選擇性91%ee得到吲哚-芳基軸手性化合物,該反應(yīng)條件溫和,官能團兼容性較好。進一步對產(chǎn)物的氧化和水解我們可以得到新型的軸手性分子骨架。第二章:利用BF3·OEt2誘導(dǎo)茂金屬烯酮經(jīng)過重排環(huán)化過程構(gòu)建了茂金屬并環(huán)已酮結(jié)構(gòu)。該反應(yīng)沒有經(jīng)歷正常的Nazarov環(huán)化生成茂金屬并環(huán)戊酮,而是生成了茂金屬并環(huán)已酮結(jié)構(gòu),我們猜測反應(yīng)可能是經(jīng)歷一個1,2-H遷移接著發(fā)生分子內(nèi)傅-克烷基化環(huán)化的過程。在研究產(chǎn)物酮的α位烷基化時還發(fā)現(xiàn)了親電試劑優(yōu)先從位阻較大的第二個Cp環(huán)同方向進攻。第三章:基于手性二酮的骨架利用C-H官能團化策略合成了具有平面手性的Pd,Ir金屬的絡(luò)合物,所合成的金屬絡(luò)合物的結(jié)構(gòu)可以通過核磁以及單晶得以確認(rèn)。此外初步研究了所得的金屬絡(luò)合物在催化氫化還原以及1,2加成反應(yīng)中的應(yīng)用。最后在NBS和Pd(OAc)2的作用下我們實現(xiàn)了對手性二酮的雙溴代反應(yīng),進而合成了新型的手性V-型結(jié)構(gòu)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 偽 -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.
【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O641.4;O621.251
本文編號：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 偽 -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.
【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O641.4;O621.251
【參考文獻】
相關(guān)期刊論文 前1條
1 張松;陸俊筑;葉金星;段偉良;;手性磷酸控制的不對稱碳?xì)浞蓟磻?yīng)合成平面手性二茂鐵化合物[J];有機化學(xué);2016年04期
，本文編號：2203809
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