Reactivity of acyclic (pentadienyl)iron(1+) cations with phosphonate stabilized nucleophiles: application to the synthesis of oxygenated metabolites of carvone

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• 作者：Do W. Lee ; Charles F. Manful ; Jayapal Reddy Gone ; Yuzhi Ma ; William A. Donaldson ; ^{william.donaldson@marquette.edu" class="auth_mail" title="E-mail the corresponding author}
• 关键词：Dienyl-iron cations ; Nucleophilic addition ; Horner&ndash ; Emmons olefination ; Cyclocarbonylation ; Terpenes
• 刊名：Tetrahedron
• 出版年：2016
• 出版时间：4 February 2016
• 年：2016
• 卷：72
• 期：5
• 页码：753-759
• 全文大小：565 K

文摘

The addition of phosphonate stabilized carbon nucleophiles to acyclic (pentadienyl)iron(1+) cations proceeds predominantly at an internal carbon to afford (pentenediyl)iron complexes. Those complexes bearing an electron withdrawing group at the σ-bound carbon (i.e., 13/14) are stable and isolable, while complexes which do not contain an electron withdrawing group at the σ-bound carbon undergo CO insertion, reductive elimination and conjugation of the double bond to afford cyclohexenone products (21/22). Deprotonation of the phosphonate 13/14 or 21 and reaction with paraformaldehyde affords the olefinated products. This methodology was utilized to prepare oxygenated carvone metabolites (±)-25 and (±)-26.