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Gold(I)-Catalyzed Reactions of exo-Glycals with Propargyl Esters toward C-1 Alkenyl Spirocyclopropyl Carbohydrates
Organic Letters ( IF 4.9 ) Pub Date : 2024-09-16 , DOI: 10.1021/acs.orglett.4c02754 Mylène Lang, Sophie Walter, Delphine Hatey, Aurélien Blanc, Philippe Compain, Nicolas Kern
Organic Letters ( IF 4.9 ) Pub Date : 2024-09-16 , DOI: 10.1021/acs.orglett.4c02754 Mylène Lang, Sophie Walter, Delphine Hatey, Aurélien Blanc, Philippe Compain, Nicolas Kern
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 exo-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.
中文翻译:
金 (I) 催化外型甘油与炔丙酯生成 C-1 烯基螺环丙基碳水化合物的反应
描述了一种用于构建新型假异头 C-1 烯基螺环丙基糖的原子经济且无重氮策略。利用金 (I) 催化下的炔丙酯的 1,2- 迁移途径,容易获得的外切糖苷以中等至优异的产率进行 β-选择性烯基类胡萝卜素插入。通过配体选择和酯的电子富集,有利于炔丙基部分的优先激活和协同[2+1]插入。还演示了使用构象偏差和重排的立体控制。
更新日期:2024-09-16
中文翻译:
金 (I) 催化外型甘油与炔丙酯生成 C-1 烯基螺环丙基碳水化合物的反应
描述了一种用于构建新型假异头 C-1 烯基螺环丙基糖的原子经济且无重氮策略。利用金 (I) 催化下的炔丙酯的 1,2- 迁移途径,容易获得的外切糖苷以中等至优异的产率进行 β-选择性烯基类胡萝卜素插入。通过配体选择和酯的电子富集,有利于炔丙基部分的优先激活和协同[2+1]插入。还演示了使用构象偏差和重排的立体控制。