Allylic activation across an Ir-Sn heterobimetallic catalyst: nucleophilic substitution and disproportionation of allylic alcohol

作者：Chatterjee Paresh Nath; Roy Sujit^*

来源：Tetrahedron, 2012, 68(19): 3776-3785.

DOI：10.1016/j.tet.2012.02.054

• Bimetallic catalyst
• Allylic activation
• Nucleophilic substitution
• Allylic alcohol
• Mechanism

A nucleophilic substitution of allylic alcohols with carbon (arene, heteroarene, allyltrimethylsilane, and 1,3-dicarbonyl compound), sulfur (thiol), oxygen (alcohol), and nitrogen (sulfonamide) nucleophiles has been demonstrated using an in house developed [Ir(COD)(SnCl3)1(mu-Cl)](2) heterobimetallic catalyst in 1,2-dichloroethane to afford the corresponding allylic products in moderate to excellent yields. In 4-hydroxycoumarin, allylation occurs at the 3-position. The diaryl-substituted allylic alcohols undergo disproportionation in presence of the heterobimetallic catalyst to provide the corresponding alkenes and chalcones. An electrophilic mechanism is proposed from Hammett correlation study.

• 出版日期2012-5-13