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

TETRAHEDRON

卷:72

Article

Lee, Do W.¹  Manful, Charles F.¹  Gone, Jayapal Reddy¹  Ma, Yuzhi¹  Donaldson, William A.¹ 

[1] Marquette Univ, Dept Chem, POB 1881, Milwaukee, WI 53201 USA

关键词: Dienyl-iron cations;    Nucleophilic addition;    Horner-Emmons olefination;    Cyclocarbonylation;    Terpenes;   

DOI  :  10.1016/j.tet.2015.12.035

来源: Elsevier

【 摘 要 】

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 sigma-bound carbon (i.e., 13/14) are stable and isolable, while complexes which do not contain an electron withdrawing group at the sigma-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. (C) 2015 Elsevier Ltd. All rights reserved.

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