拉電子基取代之8,8-dicyanoheptafulvene和給電子基不對稱"單"取代之6-(1',1'-diethylmethyl)fulvene在氯仿迴流下進行[m+n]環化加成反應之研究

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Title:	拉電子基取代之8,8-dicyanoheptafulvene和給電子基不對稱"單"取代之6-(1',1'-diethylmethyl)fulvene在氯仿迴流下進行[m+n]環化加成反應之研究 Mechanistic Studies on The Thermal [m+n] Cycloadditions of Electron-Withdrawing substituted 8,8-dicyanoheptafulvene and Electron-Donating substituted 6-(1',1'-diethylmethyl)fulvene in chloroform
Authors:	賴致融
Contributors:	應用化學研究所
Keywords:	環加成立體選擇性電子效應 CN七環立體效應 cycloaddition Diastereoselectivity Electronic Effects 8-dicyanoheptafulvene Stectseric Effects
Date:	2006
Issue Date:	2014-06-20 10:56:53 (UTC+8)
Abstract:	本論文主要在討論有關於給電子基不對稱單取代之6-(1’,1’-diethylmethyl)fulvene (2n) 和8,8-dicyanoheptafulvene (8a) 加熱進行分子間 [m+n] 環化加成反應研究；對其進行環化加成反應相互之間的反應性、立體選擇性 (Diastereoselectivity)、位置選擇性 (Periselectivity) 和位向選擇性 (Regioselectivity)，有進一步徹底而詳細的研究探討。實驗結果顯示，在60℃CHCl3迴流的高溫反應條件下，8,8-dicyanoheptafulvene (8a)和給電子基不對稱單取代之6-(1’,1’-diethylmethyl)fulvene (2n)反應，則會顯示出百分之百之 endo立體選擇性和位向選擇性與不錯之位置選擇性，進行﹝4+2﹞環化加成反應得到同向（syn）-endo-〔4+2〕環化加成生成物 20n/20n’，比例約為2:1；或是進行﹝4+2﹞環化加成反應得到反向（anti）-endo-〔4+2〕環化加成生成物 21n/21n’，比例約為1:2。 The investigation of this research involves the synthesis and intermolecular [m+n] cycloadditions of the unsymmetrically electron-rich 6-monosubstituted 6-(1’,1’-diethylmethyl)fulvene (2n) with 8,8-dicyanoheptafulvene (8a)；designed to establish the experimental analyses of the reactivity, diastereoselectivity, periselectivity, and regioselectivity of these cycloadditions. The cycloaddition reaction of 8,8-dicyanoheptafulvene (8a) with 6-(1’,1’-diethylmethyl)fulvene (2n) at 60℃ temperature gave the syn-endo-[4+2] cycloadducts 20n/20n’ in a ratio of about 2:1 and the anti-endo-[4+2] cycloadducts 21n/21n’ in a ratio of about 1:2. The present results show that these [4+2] cycloaddition reactions took place with exclusive endo diastereoselectivity and regioselectivity. Good periselectivity was also observed.
Appears in Collections:	[Department of Chemistry & Graduate Institute of Applied Chemistry ] thesis

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