五氟二醇的优化合成及通过三氟乙酸酯释放和卤化转化为α-吡喃葡萄糖。
Optimized Synthesis of a Pentafluoro--diol and Conversion to a -Glucopyranose through Trifluoroacetate-Release and Halogenation.
作者信息
Hazlitt Robert A, John Jinu P, Tran Que-Lynn, Colby David A
机构信息
Department of Chemistry, Purdue University, West Lafayette, Indiana, 47907, USA; Department of BioMolecular Sciences, University of Mississippi, Mississippi, 38677, USA.
Department of Chemistry, Purdue University, West Lafayette, Indiana, 47907, USA.
出版信息
Tetrahedron Lett. 2016 Apr 27;57(17):1906-1908. doi: 10.1016/j.tetlet.2016.03.064. Epub 2016 Mar 19.
Abstract
Pentafluoro--diols are substrates that enable the synthesis of valuable difluoromethylene-containing organic molecules through the release of trifluoroacetate. Currently, only one synthetic strategy is available to assemble these important precursors. Herein, two new synthetic strategies to a complex pentafluoro--diol are compared to the existing route, and an improved synthetic route has completed. Moreover, the first synthesis of a -glucopyranose was finished by a tandem trifluoroacetate-release halogenation/cyclization protocol.
摘要
五氟二醇是一类底物，可通过释放三氟乙酸酯来合成有价值的含二氟亚甲基有机分子。目前，组装这些重要前体只有一种合成策略。在此，将两种合成复杂五氟二醇的新策略与现有路线进行了比较，并完成了一条改进的合成路线。此外，通过串联三氟乙酸酯释放卤化/环化方案首次完成了α-吡喃葡萄糖的合成。
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J Org Chem. 2015 Feb 6;80(3):1754-63. doi: 10.1021/jo502677a. Epub 2015 Jan 20.
3
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Angew Chem Int Ed Engl. 2015 Jan 26;54(5):1646-50. doi: 10.1002/anie.201410471. Epub 2014 Dec 4.
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