铜的反应活性可被调控，以催化从糖烯立体选择性合成2-脱氧糖苷。
Copper Reactivity Can Be Tuned to Catalyze the Stereoselective Synthesis of 2-Deoxyglycosides from Glycals.
作者信息
Palo-Nieto Carlos, Sau Abhijit, Jeanneret Robin, Payard Pierre-Adrien, Salamé Aude, Martins-Teixeira Maristela Braga, Carvalho Ivone, Grimaud Laurence, Galan M Carmen
机构信息
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 3TS, United Kingdom.
Laboratoire des biomolécules (LBM), Sorbonne Université - Ecole Normale Supérieure - CNRS, 24 rue Lhomond, 75005 Paris, France.
出版信息
Org Lett. 2020 Mar 6;22(5):1991-1996. doi: 10.1021/acs.orglett.9b04525. Epub 2020 Feb 19.
We demonstrate that tuning the reactivity of Cu by the choice of oxidation state and counterion leads to the activation of both "armed" and "disarmed" type glycals toward direct glycosylation leading to the α-stereoselective synthesis of deoxyglycosides in good to excellent yields. Mechanistic studies show that Cu is essential for effective catalysis and stereocontrol and that the reaction proceeds through dual activation of both the enol ether as well as the OH nucleophile.
我们证明，通过选择氧化态和抗衡离子来调节铜的反应活性，可使“活化”型和“钝化”型糖烯都能被激活，从而实现直接糖基化反应，以良好至优异的产率α-立体选择性地合成脱氧糖苷。机理研究表明，铜对于有效催化和立体控制至关重要，并且反应是通过烯醇醚和OH亲核试剂的双重活化进行的。
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