Minbiole Emily C, Minbiole Kevin P C
Department of Chemistry, Villanova University, Villanova, PA, USA.
J Antibiot (Tokyo). 2016 Apr;69(4):213-9. doi: 10.1038/ja.2015.136. Epub 2016 Jan 6.
In the mid-1990s, Petasis reexamined a promising but infrequently used rearrangement strategy, the so-called Ferrier-type-II reaction, and provided it with a modern update. Previously, Ferrier had developed a strategy where carbohydrate derivatives would undergo a fragmentation/aldol-type recombination sequence, generating a carbocycle, albeit under the promotion of stoichiometric mercury salts. Petasis' new variant showed the promise to effectively and stereoselectively convert a range of cyclic vinyl acetals to useful tetrahydrofurans and tetrahydropyrans, using less toxic promoters. Since these first reports, the 'Petasis-Ferrier rearrangement' has represented a vibrant area of research and innovation for organic chemists. With numerous applications in complex natural product total synthesis, the utility of the reaction has been resoundingly established. Recent developments have extended the reaction to a broader synthetic context, allowing for in situ generation of rearrangement substrates and more liberal interpretation of what fragmentation/recombination reactions warrant the designation of a Petasis-Ferrier rearrangement.
20世纪90年代中期，佩塔西斯重新审视了一种有前景但很少使用的重排策略，即所谓的费里尔-II型反应，并对其进行了现代改进。此前，费里尔开发了一种策略，在化学计量的汞盐促进下，碳水化合物衍生物会经历碎片化/醛醇型重组序列，生成一个碳环。佩塔西斯的新变体显示出有望使用毒性较小的促进剂，有效且立体选择性地将一系列环状乙烯基缩醛转化为有用的四氢呋喃和四氢吡喃。自这些首次报道以来，“佩塔西斯-费里尔重排”一直是有机化学家研究和创新的活跃领域。该反应在复杂天然产物全合成中有众多应用，其效用已得到充分确立。最近的进展将该反应扩展到更广泛的合成背景中，允许原位生成重排底物，并对哪些碎片化/重组反应可称为佩塔西斯-费里尔重排有了更宽泛的解释。
