A mechanism of addition of a new aromatic electrophile, nitrobenzofuroxan, to cyclopentadiene
详细信息 查看全文
- 作者：D. V. Steglenko ; M. E. Kletsky ; S. V. Kurbatov ; V. I. Minkin ; R. Goumont and F. Terrier
- 关键词：nitrobenzofuroxans ; aromatic electrophiles ; polar cycloaddition ; zwitter ; ionic σ ; complexes ; [3 ; 3] ; sigmatropic rearrangement ; reaction indices ; quantum chemical calculations ; density functional theory
- 刊名：Russian Chemical Bulletin
- 出版年：2009
- 出版时间：August, 2009
- 年：2009
- 卷：58
- 期：8
- 页码：1602-1608
- 全文大小：394.4 KB
文摘
The reaction mechanisms of cycloaddition of nitrobenzofuroxan to cyclopentadiene are studied using DFT calculations at the B3LYP/6-31G* level in the gas phase and with account of the solvation effects. The reaction follows a three-step mechanism and includes the formation of a prereaction donor-acceptor complex, endo [4+2] cycloaddition with inverse electron demands (IED), and [3,3]-sigmatropic rearrangement to the final endo [2+4] adduct. No formation of stable bipolar σ-complexes on the minimum-energy reaction pathways occurs.