Ir-Catalyzed Chemo-, Regio-, and Enantioselective Allylic Enolization of 6,6-Dimethyl-3-((trimethylsilyl)oxy)cyclohex-2-en-1-one Involving Keto-Enol Isomerization

The utilization of 6,6-dimethyl-3-((trimethylsilyl)oxy)cyclohex-2-en-1-one made from an unsymmetrical 4,4-dimethylcyclohexane-1,3-dione in iridium-catalyzed allylic enolization involving keto-enol isomerization is accomplished under mild conditions. The chemoselectivity, regioselectivity, and enantioselectivity are facilitated by the quaternary carbon and adjusting the reaction conditions. This method provides the substituted 2-(but-3-en-2-yl)-3-hydroxy-6,6-dimethylcyclohex-2-en-1-ones in good to high yields with high level of chemo-, regio-, and enantioselectivities. The chiral carbon-fluorine bond formation is induced by an adjacent chiral carbon center of the allylated 3-hydroxy-6,6-dimethylcyclohex-2-en-1-one, as well.

Automated summary

The utilization of 6,6-dimethyl-3-((trimethylsilyl)oxy)cyclohex-2-en-1-one, derived from an unsymmetrical 4,4-dimethylcyclohexane-1,3-dione, in iridium-catalyzed allylic enolization is achieved under mild conditions. The presence of a quaternary carbon and adjustment of reaction conditions enable high selectivities in terms of chemoselectivity, regioselectivity, and enantioselectivity. This method provides substituted 2-(but-3-en-2-yl)-3-hydroxy-6,6-dimethylcyclohex-2-en-1-ones in good to high yields with excellent chemo-, regio-, and enantioselectivities. Additionally, the formation of chiral carbon-fluorine bonds is induced by an adjacent chiral carbon center.