有机催化不对称过氧化γ,δ-不饱和β-酮酯——手性环过氧化物的新途径。

School of Chemistry, University College Cork, T12 YN60 Cork, Ireland.

Analytical and Biological Chemistry Research Facility, University College Cork, T12 YN60 Cork, Ireland.

Molecules. 2023 May 24;28(11):4317. doi: 10.3390/molecules28114317.

A methodology for the asymmetric peroxidation of γ,δ-unsaturated β-keto esters is presented. Using a cinchona-derived organocatalyst, the target δ-peroxy-β-keto esters were obtained in high enantiomeric ratios of up to 95:5. Additionally, these δ-peroxy esters can be readily reduced to chiral δ-hydroxy-β-keto esters without impacting the β-keto ester functionality. Importantly, this chemistry opens up a concise route to chiral 1,2-dioxolanes, a common motif in many bioactive natural products, via a novel PO-mediated cyclisation of the corresponding δ-peroxy-β-hydroxy esters.

本文提出了一种γ,δ-不饱和β-酮酯不对称过氧化的方法。使用金鸡纳衍生的有机催化剂，可以高对映选择性（高达 95:5）获得目标 δ-过氧-β-酮酯。此外，这些 δ-过氧酯可以很容易地被还原为手性 δ-羟基-β-酮酯，而不会影响β-酮酯的官能团。重要的是，这种化学方法通过相应的 δ-过氧-β-羟基酯的新型 PO 介导环化反应，为手性 1,2-二恶烷（许多生物活性天然产物中的常见结构单元）开辟了一条简洁的合成路线。