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Author: 吳靜雯
Thesis Title: 取代基對下列分子做分子內環化反應,影響位向選擇性之理論計算研究: 1. α-Sulfenyl-, α-Sulfinyl-, α-Sulfonyl-5-(R)-5-Hexenyl Radicals 2. 2,5-Hexadienyl Radicals
Advisor: 何嘉仁
Degree: 博士
Doctor
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2007
Academic Year: 95
Language: 中文
Number of pages: 127
Keywords (in Chinese): 自由基環化反應分子內
Thesis Type: Academic thesis/ dissertation
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  • 本論文藉由理論計算的方法,在UB3LYP/6-31G(d)的計算層級下對各穩定點的結構做幾何優選,探討取代基對於α-sulfenyl-, α-sulfinyl-, and α-sulfonyl-5-(R)-5-hexenyl radicals以及2,5-hexadienyl radicals分子內環化反應的影響,以下將分為兩部分進行討論:

    第一部分:
    α-sulfinyl-5-hexenyl radicals在形成環狀產物時顯示了高位向選擇性,其生成五員環與六員環的產物比例為94.0/6.0,而在α-sulfenyl-, and α-sulfonyl-5-hexenyl radicals中環化形成六員環的比例較高。相反的,在C5接上甲基後產物則變成六員環,而其他的取代基如拉電子基的CN、NO2或者是推電子基的NH2等反應的主產物也是形成六員環,其中當反應物為α-sulfonyl-5-amine-5-hexenyl radicals時,經由計算後得到六員環的比例為100,為選擇性最高的反應物。

    第二部分:
    當不同種類的取代基如CN、NO2、CH3、NH2以及tert-butyl等取代在2,5-hexadienyl radicals的C1、C5以及C6位置上時,其對於分子內環化反應有不同效應的影響。當推電子基在C1上時,自由基的SOMO軌域能量會上升,進而增加與LUMO軌域之間的作用力,相反的拉電子基則會使SOMO軌域能量下降,進而增加與HOMO軌域之間的作用力。而上述的兩種作用力使得反應的活化能降低了0.9〜10.2 kcal/mol,使反應速率增加了3〜2.7 × 107倍。相似的作用力也發生在C6的位置,而反應的活化能降低了0.2-4.8 kcal/mol,反應速率則增加了2〜2800倍。而當取代基接在C5時則因為立障效應使產物變為六員環。最後,我們嘗試將雙取代基取代在C1以及C6的位置,並討論capto-dative effect對環化反應的影響,結果顯示拉電子基雙取代使活化能下降的較多。

    We carried out the DFT calculation of intramolecular cyclization reaction of α-sulfenyl-, α-sulfinyl-, α-sulfonyl-5-(R)-5-hexenyl radicals and 2,5-hexadienyl radicals by density functional theory. All of the local minimum structures are optimized with 6-31G(d) basis set at the levels of UB3LYP. There are two sections rendered here.

    Section 1:
    The α-sulfinyl-5-hexenyl radical exhibits unexpected regioselectivity (94.0:6.0) via the 5-exo mode, whereas the α-sulfenyl- and α-sulfonyl-5-hexenyl radicals show increasing branching ratios of the 6-endo product. In contrast, the cyclization of the α-sulfur-based 5-methyl-substituted counterparts yields essentially the 6-endo products in all cases; in particular, the α-SO2-5-CH3-5-hexenyl radical gives high regioselectivity (98.8:1.2) via the 6-endo mode. Several other 5-substituted moieties, including the electron-withdrawing – CN and NO2 – or electron-donating substituents – NH2 – also proceed preferentially to 6-endo closure. The α-sulfonyl- 5-amine-5-hexenyl radical is calculated to proceed exclusively the 6-endo product, a demonstration of the high synthetic value of the reaction.

    Section 2:
    Various substituents – CN, NO2, CH3, NH2, and tert-butyl – at various positions – C1, C5 and C6 – were considered in the calculations. An electron-donating substituent on the C1 position raises the radical SOMO energies to increase the interaction with the alkene LUMO, whereas an electron-withdrawing counterpart lowers the SOMO and increases the interaction with the alkene HOMO. Both interactions decrease the activation energies, by 0.9 to 10.2 kcal/mol, and increase the rate of reaction rate, from 3 to 2.7 × 107 times. Similar results were obtained for the substituents at the C6 position, and the activation energies for the intramolecular cyclization were decreased by 0.2 - 4.8 kcal/mol and the reaction rate increased from 2 to 2800 times. The substituent at the C5 position favors the formation of a 6-endo product because of a steric effect. The effects of disubstituents at both C1 and C6 positions were also investigated; the results showed that the electron-withdrawing groups decrease most effectively the activation energies. The so-called captodative effect was also investigated.

    總 目 錄 中文摘要………………………………………………………………..ⅳ 英文摘要………………………………………………………………..ⅵ 第一章 緒論 1-1 簡介……………………………………………………………...1 第二章 計算原理與方法 2-1 Marcus Theory ........................................................................12 2-2 層級測試及討論.......................................................................14 第三章 取代基對分子內環化反應α-Sulfenyl-, α-Sulfinyl-, and α-Sulfonyl-5-R-5-hexenyl Radicals其位向選擇性的影響之理論計算研究 3-1 前言.......................................................................................... 17 3-2 結果與討論 3-2-1 α-sulfenyl、α-sulfinyl以及α-sulfonyl-5-hexenyl radicals的環化反應..................................................................................20 3-2-2 α-sulfenyl-5-(R)-5-hexenyl radical在C5上改變不同取代基對環化反應的影響..........................................................28 3-2-3 α-sulfinyl-5-(R)-5-hexenyl radical在C5上改變不同取代基對環化反應的影響..........................................................36 3-2-4α-sulfonyl-5-(R)-5-hexenyl radical在C5上改變不同取代基對環化反應的影響..........................................................44 第四章 在不同的反應位置上取代基效應對於分子內環化反應2,5-Hexadienyl Radicals的影響之理論計算研究 4-1 前言............................................................................................53 4-2 結果與討論 4-2-1 2,5-Hexadienyl自由基分子內環化反應之研究....................55 4-2-2 2,5-Hexadienyl自由基在C1上接上取代基之分子內環化反應研究..............................................................................59 4-2-3 2,5-Hexadienyl自由基在C5上接上取代基之分子內環化反應研究.............................................................................70 4-2-4 2,5-Hexadienyl自由基在C6上接上取代基之分子內環化反應研究..............................................................................77 4-2-5 2,5-Hexadienyl自由基在C1與C6分別接上雙取代基之分子內環化反應研究........................................................ .90 4-2-6 2,5-Hexadienyl自由基在C1與C6分別接上單取代與雙取代基後其rate coefficient以及relative rate之研究.......96 第五章 總結..........................................................................................103 參考文獻................................................................................................110 附錄........................................................................................................115

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