通过 2-吲哚三氟甲磺酸酯的氧化还原接力 Heck 反应实现吲哚的对映选择性 C2-烷基化反应。
Enantioselective C2-Alkylation of Indoles through a Redox-Relay Heck Reaction of 2-Indole Triflates.
机构信息
Department of Chemistry, University of Utah, 315 S 1400 E, Salt Lake City, Utah, 84112, USA.
出版信息
Chemistry. 2019 Jan 7;25(2):512-515. doi: 10.1002/chem.201805416. Epub 2018 Dec 11.
Abstract
A palladium-catalyzed enantioselective redox-relay Heck reaction of 2-indole triflates and disubstituted alkenes is reported. This process combines readily available indole triflates with a variety of alkenes to afford a range of indole derivatives bearing a stereocenter adjacent to C2. Enantioselectivity is achieved through use of a simple pyridine-oxazoline ligand. Tuning the electronics of the indole, through judicious choice of N-protecting group, is required to ensure selective β-hydride elimination away from the indole core. Utility of this method is highlighted in a modular formal synthesis of an S1P agonist precursor developed by Merck.
摘要
报道了钯催化的对映选择性氧化还原接力 Heck 反应，涉及 2-吲哚三氟甲磺酸酯和取代的烯烃。该过程将易得的吲哚三氟甲磺酸酯与各种烯烃结合，得到一系列在 C2 位具有立体中心的吲哚衍生物。通过使用简单的吡啶-噁唑啉配体实现了对映选择性。通过明智地选择 N-保护基来调整吲哚的电子性质，以确保β-氢消除远离吲哚核心的选择性。该方法在默克公司开发的 S1P 激动剂前体的模块化形式合成中得到了很好的应用。
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