双硫脲催化的β-选择性2-脱氧和2,6-二脱氧葡萄糖基化反应
β-Selective 2-Deoxy- and 2,6-Dideoxyglucosylations Catalyzed by Bis-Thioureas.
作者信息
Beyer Peyton D, Nielsen Michael M, Picazo Elias, Jacobsen Eric N
机构信息
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
出版信息
J Am Chem Soc. 2024 Oct 9;146(40):27318-27323. doi: 10.1021/jacs.4c11560. Epub 2024 Sep 30.
Abstract
We present methods for β-selective 2-deoxy- and 2,6-dideoxyglucosylations of natural products, carbohydrates, and amino acids using bis-thiourea hydrogen-bond-donor catalysts. Disarming ester protecting groups were necessary to counter the high reactivity of 2-deoxyglycosyl electrophiles toward non-stereospecific S1 pathways. Alcohol and phenol nucleophiles with both base- and acid-sensitive functionalities were compatible with the catalytic protocol, enabling access to a wide array of 2-deoxy-β--glucosides.
摘要
我们展示了使用双硫脲氢键供体催化剂对天然产物、碳水化合物和氨基酸进行β-选择性2-脱氧和2,6-二脱氧葡萄糖基化的方法。去除酯保护基对于对抗2-脱氧糖基亲电试剂对非立体特异性S1途径的高反应性是必要的。具有碱敏和酸敏官能团的醇和酚亲核试剂与催化方案兼容，能够合成多种2-脱氧-β-葡萄糖苷。
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