Asymmetric Robinson-Type Annulation Reaction between β‑Ketoamides and α,β-Unsaturated Ketones

Enantioselective
Robinson-type annulation reaction between β-ketoamide
and α,β-unsaturated ketone was developed by utilizing
the amino acid derived primary–secondary diamine catalysts.
The less reactive acyclic β-ketoamides employed as both electrophile
and nucleophile are reported in this asymmetric tandem reaction. A
number of chiral cyclohexenone derivatives containing an amide group
were obtained in high yields and good selectivities.

本研究采用氨基酸衍生的伯-仲二胺催化剂(amino acid derived primary–secondary diamine catalysts)，成功开发了β-酮酰胺(β-ketoamide)与α,β-不饱和酮(α,β-unsaturated ketone)之间的对映选择性罗宾逊型环化反应(enantioselective Robinson-type annulation reaction)。本研究报道了在该不对称串联反应中使用反应活性较低的非环状β-酮酰胺，其可同时充当亲电试剂与亲核试剂。最终以较高收率与良好的选择性得到了一系列含酰胺基团的手性环己烯酮衍生物(chiral cyclohexenone derivatives)。