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研究生：	張翔凱 Chang, Hsiang-Kai
論文名稱：	理論計算模擬有機立體化學反應路徑與選擇性 Theoretical Calculations of Organic Stereochemistry Reaction Pathway and Selectivity
指導教授：	蔡明剛 Tsai, Ming-Kang
學位類別：	碩士 Master
系所名稱：	化學系 Department of Chemistry
論文出版年：	2020
畢業學年度：	108
語文別：	中文
論文頁數：	45
中文關鍵詞：	Gaussian 09 、立體化學、質子化反應、勢能面掃描
英文關鍵詞：	Gaussian 09, stereochemistry, protonation, potential energy surface scan
DOI URL：	http://doi.org/10.6345/NTNU202000206
論文種類：	學術論文
相關次數：	點閱：99 下載：25
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理論計算用於預測、尋找立體化學的位向選擇已行之有年，透過計算我們對微觀現象有了更進一步的了解。本篇研究以Gaussian 09為計算軟體，分為兩部分探討立體化學的反應位向，第一部份探討質子化反應(protonation)的立體位向選擇，並以不同的酸性分子：4-nitrophenol、acetic acid以及hydronium ion進行質子化反應，分子結構先以B97XD/6-31G初步優化，再以wB97XD/6-311G(d,p)做二次優化，透過分析電荷分布與過去的文獻中1，找到N-oxide與C3是可能被質子化的反應位向，以勢能面掃描與分子結構探討，說明C3的Si-face為本實驗質子化選擇性的依據，並與前人提出Re-face的選擇性進行結構比較2。最後確認反應步驟中的質子化反應與開環反應並非同步，是先進行質子化後再進行開環反應，且速率決定步驟應為開環反應，完成反應路徑分析。
第二部分探討不同配位基的Rh催化劑所產生立體產物的選擇，以及反應路徑的探討，若配位基為COD(1,5-Cyclooctadiene)，則立體產物為外消旋；若配位基為4,7,7-trimethyl-2,5-biphenylbicyclo[2.2.1]hepta-2,5-diene，則立體產物為R form，後者為我們主要的分析對象。從結構與產物的關係來判斷中間物與催化劑的可能催化位向，以B3LYP/6-31G*/SDD進行結構優化，發現可能的催化位向為between與conjugate位，再以這兩個位向進行勢能面掃描，找到between位是較為合理的催化路徑，且從掃描的能障與過渡態分子結構，支持實驗所觀察到的R form選擇性。最後再將配位基換成COD進行between位的催化反應，所得的能障也支持實驗所觀察到的外消旋。

Theoretical calculations have been used to predict and determine the possible orientation of organic and inorganic stereochemistry for a long time. It is especially suitable for investigating the transition state structures and reaction mechanism. This thesis study is an example of using Gaussian 09, a conventional computational chemistry package, to study the stereochemistry of an organic and inorganic reaction.
In the first part, we discuss the orientation of protonation by using different acids, like 4-nitrophenol, acetic acid, and hydronium ion. All structures in this part are initially optimized at the B97XD/6-31G level, and then re-optimization by using wB97XD/6-311G(d,p). Through analyzing the charge and previous literature1, we find out N-oxide and C3 is the most probable direction for protonation. The potential energy surface scanning and molecular structure are discussed, which shows that Si-face of C3 is the direction for protonation selectivity in the experiment, and compares with the early proposed Re-face structure2. Finally, we have shown that the protonation step and the ring-opening step are asynchronous, and the ring-opening step is carried out after protonation. By using frequency analysis, the rate determining step should be a ring-opening reaction.
In the second part, we discuss the selection of stereoisomers generated by Rh catalyst with different ligands. If the ligand is COD(1,5-Cyclooctadiene), the stereo product is racemic. If the ligand is 4,7,7-trimethyl-2,5-biphenylbicyclo[2.2.1]hepta-2,5- diene, the stereo product is R form, which is the main object we discuss. From the structure of intermediate and Rh catalyst, we determine some possible catalytic intermediates. All structures in this part were optimized at B3LYP/6-31G*/ SDD level. And we find out the possible catalytic directions may “between” and “conjugate”. Scanning the potential energy surface with these two directions, we find “between” is a reasonable catalytic path. And from the energy barrier and transition state structure, we support the experimental observation of R form selectivity. Finally, the ligand was replaced by COD to catalyze at the “between” position, the barrier also supports racemic observed in the experiment.

第一章 緒論   1
1-1 前言   1
1-2 文獻討論   2
1-3 研究目的   5

第二章 計算方法與實驗背景   6
2-1 幾何優化(Optimization)   6
2-2 單點能量(Single Point Energy)   7
2-3 勢能面掃描(Potential Energy Surface Scan)   7
2-4 溶劑效應(Solvent effect)   8
2-5 Gaussian 09   9
2-5-1 本文使用的計算方法   9
2-6 第一部分實驗背景   10
2-7 第二部分實驗背景   13

第三章 結果與討論   16
3-1 質子化反應路徑分析   16
3-1-1 中間物光學異構物分析   17
3-1-2 質子化反應的路徑預測   18
3-1-3 質子化反應(protonation)   19
3-1-4 過渡態結構分析(TS)   20
3-1-5 N-oxide位向質子化反應   22
3-1-6 質子化反應與開環反應的順序   23
3-2 以不同配位基的Rh催化劑進行立體選擇性   25
3-2-1 中間物與Rh催化劑的結構分析   26
3-2-2 催化劑鍵結於中間物的結構分析   27
3-2-3 合環路徑分析   36
3-2-4 不同配位基的比較   40

第四章 結論   42
參考文獻   44
                                

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