Lang Mylène, Walter Sophie, Hatey Delphine, Blanc Aurélien, Compain Philippe, Kern Nicolas
Laboratoire d'Innovation Moléculaire et Applications (LIMA), Université de Strasbourg/Université de Haute-Alsace/CNRS (UMR 7042), Equipe de Synthèse Organique et Molécules Bioactives (SYBIO), ECPM, 25 rue Becquerel, 67087 Strasbourg, France.
Institut de Chimie (UMR 7177), Université de Strasbourg, Laboratoire de Catalyse Organométallique, Synthèse organique et Santé (COSyS), 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg, France.
Org Lett. 2024 Sep 27;26(38):8017-8022. doi: 10.1021/acs.orglett.4c02754. Epub 2024 Sep 16.
An atom-economic and diazo-free strategy for the construction of novel pseudo anomeric C-1 alkenyl spirocyclopropyl sugars is described. Leveraging the 1,2-migration pathway of propargyl esters under gold(I) catalysis, easily available -glycals undergo β-selective alkenylcarbenoid insertion in moderate to excellent yields. Preferential activation of propargyl moieties and concerted [2 + 1] insertion are both favored through ligand choice and electron enrichment of esters. Stereocontrol using conformational bias and rearrangement are also demonstrated.
本文描述了一种构建新型异头碳-1烯基螺环丙基糖的原子经济且无重氮的策略。利用金（I）催化下炔丙基酯的1,2-迁移途径，易于获得的β-糖苷可发生β-选择性烯基卡宾插入反应，产率中等至优异。通过配体选择和酯的电子富集，炔丙基部分的优先活化和协同的[2 + 1]插入均受到青睐。还展示了利用构象偏向和重排进行立体控制的方法。
