Substituted 5,6,11,12-Tetradehydrodibenzo[a,e]cyclooctenes: Syntheses, Properties, and DFT Studies of Substituted Sondheimer鈥揥ong Diynes

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• 作者：Feng Xu ; Lifen Peng ; Kenta Shinohara ; Takamoto Morita ; Suguru Yoshida ; Takamitsu Hosoya ; Akihiro Orita ; Junzo Otera
• 刊名：Journal of Organic Chemistry
• 出版年：2014
• 出版时间：December 5, 2014
• 年：2014
• 卷：79
• 期：23
• 页码：11592-11608
• 全文大小：784K
• ISSN：1520-6904

文摘

Highly strained cyclic acetylenes 5,6,11,12-tetradehydrodibenzo[a,e]cyclooctenes (Sondheimer鈥揥ong diynes) having various substituents on their benzene rings were synthesized successfully by one-pot treatment of the corresponding formyl sulfones with diethyl chlorophosphate/lithium hexamethyldisilazide (LiHMDS) and then lithium diisopropylamide (LDA). When mixtures of two types of formyl sulfones bearing different substituents were subjected to this protocol, the unsymmetrically substituted Sondheimer鈥揥ong diynes could be synthesized in a stepwise manner by isolation of the heterocoupled vinyl sulfone intermediates followed by their treatment with LDA. The UV鈥搗is absorption spectra and cyclic voltammograms of the substituted Sondheimer鈥揥ong diynes were recorded. The electronic effect of substituents on the diynes was investigated in their click reactions and nucleophilic and electrophilic additions.