Andreev Ivan A, Ratmanova Nina K, Novoselov Anton M, Belov Dmitry S, Seregina Irina F, Kurkin Alexander V
Department of Chemistry, Lomonosov Moscow State University, Leninsky Gory 1/3, 119991, Moscow, Russia.
Chemistry. 2016 May 17;22(21):7262-7. doi: 10.1002/chem.201600273. Epub 2016 Apr 14.
A facile one-pot approach based on a thermally induced metal- and solvent-free 5-endo-dig cyclization reaction of the amino propargylic alcohols in combination with Dess-Martin periodinane-promoted oxidative dearomatization of 4,5,6,7-tetrahydroindole intermediates provides an efficient and robust access to 5,6-dihydro-1H-indol-2(4H)ones. Green, relatively mild and operationally simple characteristics of the synthetic sequence are the major advantages, which greatly amplify the developed methodology. The utility of obtained indolones as unified key precursors is demonstrated by the application of these products to the formal total syntheses of a whole pleiad of Erythrina- and Lycorine-type alkaloids, namely (±)-erysotramidine, (±)-erysotrine, (±)-erythravine, (±)-γ-lycorane, and abnormal erythrinanes (±)-coccoline and (±)-coccuvinine.
一种简便的一锅法，基于氨基炔丙醇的热诱导无金属和无溶剂的5-内型-环化反应，并结合戴斯-马丁高碘烷促进的4,5,6,7-四氢吲哚中间体的氧化脱芳构化反应，为合成5,6-二氢-1H-吲哚-2(4H)酮提供了一种高效且可靠的方法。该合成路线具有绿色、相对温和且操作简单的特点，这是其主要优势，极大地扩展了所开发的方法。通过将这些产物应用于多种刺桐属和石蒜碱型生物碱的形式全合成，即(±)-刺桐曲胺、(±)-刺桐碱、(±)-刺桐文碱、(±)-γ-石蒜烷以及异常刺桐烷类(±)-可可林和(±)-可可维宁，证明了所获得的吲哚酮作为统一关键前体的实用性。
