臺灣博碩士論文加值系統

本論文之研究，旨在改變heptafulvenes與 fulvenes的環外取代基8,8-dicyanoheptafulvene (9a) 與2-(2,4- cyclopentadien -1-ylidene) -1,3-dithiolanefulvene (3c) 加熱進行分子間 [m+n]環化加成反應,進而瞭解影響其鍵結之過渡狀態的立體效應 ( Steric Effects) 與電子效應 ( Electronic Effects )，以及對環化加成反應的立體選擇性 ( Diastereoselectivity )、位置選擇性 ( Periselectivity ) 和位向選擇性 ( Regioselectivity ) 之影響性的反應機構研究。
〝強〞缺電子基取代之 8,8 -dicyanoheptafulvene ( 9a )(LUM0) 與 2- (2,4-cyclopentadien-1-ylidene) -1,3-dithiolane-
fulvene ( 3c ) (HOMO)加熱進行反應,只得到 [4+2] 之環化加成生成物 20a,b ( 1.58 : 1 )，產率65%。

In order to determine the product selectivity，such as the
diastereoselectivity，periselectivity，and regioselectivity，which is governed by steric effects and electronic effects of the exocyclic substituents on the fulvenes and heptafulvenes，the intermolcular cycloadditions of electron-rich disubstituted 2- (2，4-cyclopentien-1-ylidene)-1，3-dithiolanefulvene (3c)，with 8，8-dicyanoheptafulvene (9a) are investigated.
The reaction of strong electron-deficient substituted heptafulvene 9a (LUMO) with the fulvene 3c (HOMO) afford [4+2] adducts 20a (syn) and 20b (anti) in a ratio of about 1.58：1 in 65％ yield.

摘要．．．．．．．．．．．．．．．．．．．．．．I
Abstract．．．．．．．．．．．．．．．．．．．． II
光譜目錄．．．．．．．．．．．．．．．．．．．．III
表目錄．．．．．．．．．．．．．．．．．．．．．IV
圖目錄．．．．．．．．．．．．．．．．．．．．．V
緒論．．．．．．．．．．．．．．．．．．．．．．1
結果與討論．．．．．．．．．．．．．．．．．．．21
結論．．．．．．．．．．．．．．．．．．．．．．39
實驗步驟．．．．．．．．．．．．．．．．．．．．42
參考文獻．．．．．．．．．．．．．．．．．．．．47

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