Regioselective electrophilic addition vs epoxidation of mCPBA towards anti-Bredt olefin of fulleroid

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• 作者：Naohiko Ikuma ; ^{ikuma@chem.eng.osaka-u.ac.jp} ; Satoko Sumioka ; Haruyasu Asahara ; Takumi Oshima ; ^{oshima@chem.eng.osaka-u.ac.jp}
• 关键词：YFPRMYKUGGTPKR-UHFFFAOYSA-N ; OGJLAKGDHZTZPQ-UHFFFAOYSA-N ; FYWICFYPZDACDG-UHFFFAOYSA-N
• 刊名：Tetrahedron Letters
• 出版年：2012
• 期刊代码：109_00404039
• 类别：ch
• 出版时间：11 July, 2012
• 卷：53
• 期：28
• 页码：3581-3584
• 文件大小：579 K

摘要

The mCPBA oxidation of methano-bridged [5,6] open fulleroid trong class="boldFont">1trong> anomalously resulted in the selective electrophilic addition at the bridgehead anti-Bredt double bond rather than the usual epoxidation. The mechanistic preference for the unprecedented stepwise addition of mCPBA vs the concerted epoxidation was explained in terms of the notable 蟺-orbital misalignment (>30掳) based on the B3LYP/6-31G(d) level calculation.