臺灣博碩士論文加值系統

本研究運用半經驗及ab initio的量子力學理論計算方法研究5-substituted-2-dicyanomethyleneadamantanes及5-aza-2-dicyanomethyleneadamantane N-oxide分別與CH3MgCl及PhCH2MgCl反應之π面選擇性，所探討的取代基包含-F, -Cl, -Br, -OH, -NH2, -OMgCl, -CH3及-Si(CH3)3，結果顯示，除了-Si(CH3)3外，其餘取代基化合物皆較易進行syn的反應，而計算所得-F, -Cl, -Br之syn/anti attack的產物比例與實驗有很好的一致性，在所用的PM3, HF及B3LYP方法中，HF的方法與實驗的一致性最好。
此外，由NBO分析方法發現，與親核劑CH3MgCl的反應中，過渡態之hyperconjugative σCα-Cβ→σ*C-Nu interactions造成的穩定化能量與π面選擇性有高相關度；在與PhCH2MgCl的反應中，-F, -Cl, -Br之結果顯示，由σCα-Cβ→π*C-C超共軛作用力造成的穩定化能量是影響π面選擇性的一重要因素，而-OH及-NH2之π面選擇性除了與上述超共軛效應有關，取代基與PhCH2MgCl之苯環間的靜電作用力亦是一重要因素，-OMgCl則主要由Mg與苯環的靜電作用力決定面的選擇性。在5-aza-2-dicyanomethyleneadamantane N-oxide與Grignard reagents的反應中，除了上述的超共軛效應外，結構效應亦是影響π面選擇性的一重要因素。

The π-facial selectivity in the reactions of 5-substituted-2-dicyanomethyleneadamantanes and 5-aza-2-dicyanomethyleneadamantane N-oxide with the Grignard reagents, CH3MgCl and/or PhCH2MgCl were examined using semiempirical and ab initio calculation. The substituents investigated include -F, -Cl, -Br, -OH, NH2, -OMgCl, -CH3 and -Si(CH3)3. The reactions for all substituents, except the -Si(CH3)3 group, favor syn attack. The calculated syn/anti product ratio for the substituents of -F, -Cl, -Br groups agree well with available experimental results. The results obtained from the PM3, HF and B3LYP methods show that the HF results agree with the experimental results better than the other two methods.
In addition, the results of employed NBO analysis show that the stabilization energy due to the hyperconjugative σCα-Cβ→σ*C-Nu interactions at the transition state correlates well withπ-facial selectivity in the reactions of 5-substituted-2-dicyanomethyleneadamantanes with CH3MgCl. The calculated results for the reaction with PhCH2MgCl appear that the strength of the hyperconjugative σCα-Cβ→π*C-C interactions at the transition state plays a significant role in π-facial selectivity for the substituents of -F, -Cl, -Br groups. Besides the hyperconjugation described above, the electrostatic interactions between the benzyl group of PhCH2MgCl and -OH and/or -NH2 groups in the 5-substituted-2-dicyanomethyleneadamantanes are also a significant factor in the π-facial selectivity. The calculations of 5-aza-2-dicyanomethyleneadamantane N-oxide also gave results that structural effects, as found in previous study, affect the syn/anti product ratio significantly in the π-facial selectivity.

第一章 緒論1
1-1金剛烷 1
1-2金剛烷衍生物面選擇性的研究2
1-3其他系統之面選擇性的相關研究6
1-4本研究的目標8
第二章 方法10
2-1 金剛烷衍生物及其與Grignard reagents反應的過渡態 10
2-1.1 金剛烷衍生物與CH3MgCl反應的過渡態10
2-1.2 金剛烷衍生物與PhCH2MgCl反應的過渡態14
2-1.3 金剛烷衍生物本身之計算14
2-2 自然分佈分析和自然鍵結軌域分析15
2-2.1 簡介15
2-2.2 自然鍵結軌域分析18
2-2.2.1 建構NAOs的方法18
2-2.2.2 最大佔據混成和自然混成22
第三章 結果與討論26
3-1 5-substituted-2-dicyanomethyleneadamantanes與Grignard reagent CH3MgCl的反應27
3-1.1計算結果與實驗結果的比較27
3-1.2 NPA及NBO計算結果分析35
3-1.3用NBO分析方法探討超共軛作用力46
3-1.4過渡態結構53
3-2 5-substituted-2-dicyanomethyleneadamantanes與Grignard reagent PhCH2MgCl的反應60
3-2.1計算結果與實驗結果及CH3MgCl的結果比較60
3-2.2過渡態結構67
3-2.3 NPA計算結果分析72
3-2.4用NBO分析方法探討超共軛作用力76
3-3 5-aza-2-dicyanomethyleneadamantane N-oxide與Grignard reagents CH3MgCl及PhCH2MgCl的反應82
3-3.1 5-aza-2-dicyanomethyleneadamantane N-oxide與CH3MgCl的反應82
3-3.2 5-aza-2-dicyanomethyleneadamantane N-oxide與PhCH2MgCl的反應88
3-4 5-substituted-2-dicyanomethyleneadamantanes90
3-4.1電荷分析90
3-4.2用NBO分析方法探討超共軛作用力90
3-4.3混成軌域94
3-4.4結構分析98
第四章 結論101
參考文獻103

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