天堂国产午夜亚洲专区-少妇人妻综合久久蜜臀-国产成人户外露出视频在线-国产91传媒一区二区三区

當(dāng)前位置:主頁 > 科技論文 > 化學(xué)論文 >

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

【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

資料下載
論文發(fā)表

本文鏈接:http://sikaile.net/kejilunwen/huaxue/2203809.html


Copyright(c)文論論文網(wǎng)All Rights Reserved | 網(wǎng)站地圖 |

版權(quán)申明:資料由用戶00f6c***提供,本站僅收錄摘要或目錄,作者需要刪除請E-mail郵箱bigeng88@qq.com
亚洲精品福利入口在线| 日韩高清中文字幕亚洲| 亚洲二区欧美一区二区| 亚洲中文在线中文字幕91| 日韩欧美第一页在线观看| 亚洲av熟女一区二区三区蜜桃 | 视频在线观看色一区二区| 很黄很污在线免费观看| 成年人黄片大全在线观看| 欧美大胆美女a级视频| 成在线人免费视频一区二区| 黄片在线观看一区二区三区| 中文字幕五月婷婷免费| 欧美一区日韩一区日韩一区| 亚洲一区二区亚洲日本| 国产日韩精品欧美综合区| 精品人妻久久一品二品三品| 五月综合婷婷在线伊人| 亚洲精品国产主播一区| 国产欧美高清精品一区| 中文字幕人妻一区二区免费| 婷婷激情五月天丁香社区 | 国产在线视频好看不卡| 国产午夜精品久久福利| 亚洲男女性生活免费视频| 老鸭窝老鸭窝一区二区 | 久久综合日韩精品免费观看| 精品al亚洲麻豆一区| 亚洲一区二区三区国产| 国产大屁股喷水在线观看视频| 国产麻豆成人精品区在线观看| 亚洲中文字幕视频在线播放| 91精品日本在线视频| 欧美成人免费视频午夜色| 国产日产欧美精品视频| 精品欧美国产一二三区| 亚洲欧美日韩国产综合在线| 国产性色精品福利在线观看| 免费精品一区二区三区| 大香伊蕉欧美一区二区三区| 久久国产亚洲精品赲碰热|