Selectivity in Garratt鈭払raverman Cyclization: An Experimental and Computational Study

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• 作者：Manasi Maji ; Dibyendu Mallick ; Sayantan Mondal ; Anakuthil Anoop ; Subhendu Sekhar Bag ; Amit Basak ; Eluvathingal D. Jemmis
• 刊名：Organic Letters
• 出版年：2011
• 出版时间：March 4, 2011
• 年：2011
• 卷：13
• 期：5
• 页码：888-891
• 全文大小：775K
• 年卷期：v.13,no.5(March 4, 2011)
• ISSN：1523-7052

文摘

Bispropargyl sulfones equipped with aromatic rings of dissimilar nature were synthesized. Under basic conditions, these sulfones isomerized to the bisallenic sulfones, creating a competitive scenario between two alternate Garratt鈭払raverman (GB) cyclization pathways. The observed product distribution ruled out the involvement of any ionic intermediate and supported the diradical mechanism with greater involvement of the electron-rich aromatic ring via the more nucleophilic radical. DFT-based calculations supported the diradical mechanism along with the observed selectivity.