N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation.
D. I. Mendeleev University of Chemical Technology of Russia, Moscow, Russian Federation.
Angew Chem Int Ed Engl. 2018 Mar 19;57(13):3372-3376. doi: 10.1002/anie.201712651. Epub 2018 Feb 23.
The instability of hydroxy peroxyesters, the elusive Criegee intermediates of the Baeyer-Villiger rearrangement, can be alleviated by selective deactivation of the stereoelectronic effects that promote the 1,2-alkyl shift. Stable cyclic Criegee intermediates constrained within a five-membered ring can be prepared by mild reduction of the respective hydroperoxy peroxyesters (β-hydroperoxy-β-peroxylactones) which were formed in high yields in reaction of β-ketoesters with BF ⋅Et O/H O .
过氧羟酯的不稳定性，即 Baeyer-Villiger 重排的难以捉摸的 Criegee 中间体，可以通过选择性失活促进 1,2-烷基迁移的立体电子效应来缓解。通过温和还原相应的过氧过氧酯（β-过氧-β-过氧内酯）可以制备稳定的环状 Criegee 中间体，β-酮酯与 BF ⋅Et O/H O 反应以高产率形成了这些过氧过氧酯。
