通过内消旋二酮的野依不对称去对称化高效、可扩展地合成环氧喹啉。
Efficient, scalable asymmetric synthesis of an epoxy quinol via Noyori desymmetrization of a meso diketone.
作者信息
Clay David R, Rosenberg Ashley G, McIntosh Matthias C
机构信息
Department of Chemistry and Biochemistry, University of Arkansas, Fayetteville, AR 72701, USA.
出版信息
Tetrahedron Asymmetry. 2011 Apr 10;22(7):713-716. doi: 10.1016/j.tetasy.2011.04.022.
Abstract
Epoxy quinol 1a was prepared on a multi-gram scale by Noyori transfer hydrogenative desymmetrization of the readily available meso epoxy diketone 4. Although the intrinsic enantioselectivity for the desymmetrization was modest (82:18 er at 4% conversion), a highly enantiopure product (99.6:0.4 er) could be obtained in one operation in 44% yield via kinetic resolution of the minor enantiomer with long reaction times (48 h), or in 73% yield by combination with an enzymatic resolution of a 93:7 er mixture.
摘要
环氧喹诺酮1a是通过对易于获得的内消旋环氧二酮4进行野依转移氢化去对称化反应，以多克规模制备的。尽管去对称化反应的固有对映选择性一般（4%转化率时对映体比例为82:18），但通过延长反应时间（48小时）对次要对映体进行动力学拆分，一次操作即可获得高对映体纯度的产物（对映体比例为99.6:0.4），产率为44%；或者与对映体比例为93:7的混合物进行酶促拆分相结合，产率为73%。
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本文引用的文献
1
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Biosci Biotechnol Biochem. 1992 Jan;56(5):810-1. doi: 10.1271/bbb.56.810.
2
Chemoenzymatic access to versatile epoxyquinol synthons.
Org Lett. 2009 Oct 1;11(19):4290-3. doi: 10.1021/ol9016657.
3
Toward the Synthesis of Antascomicin B. Synthesis of a Model of the C22-C34 Fragment via Ireland-Claisen and Allylic Diazene Rearrangements.
Tetrahedron. 2008;64(29):7021-7025. doi: 10.1016/j.tet.2008.05.070.
4
Tandem enyne metathesis-metallotropic [1,3]-shift for a concise total syntheses of (+)-asperpentyn, (-)-harveynone, and (-)-tricholomenyn A.
Org Lett. 2009 Feb 5;11(3):571-4. doi: 10.1021/ol802675j.
5
Conversion of Torgov's synthesis of estrone into a highly enantioselective and efficient process.
J Am Chem Soc. 2007 Aug 29;129(34):10346-7. doi: 10.1021/ja0742434. Epub 2007 Aug 2.
6
Enantioselective synthesis of natural polyoxygenated cyclohexanes and cyclohexenes from [(p-tolylsulfinyl)methyl]-p-quinols.
Chemistry. 2007;13(4):1064-77. doi: 10.1002/chem.200601330.
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Chem Commun (Camb). 2006 Sep 14(34):3634-6. doi: 10.1039/b606864b. Epub 2006 Jul 27.
8
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Preparation of new chiral building blocks: highly enantioselective reduction of prochiral 1,3-cycloalkanediones possessing a methyl group and a protected hydroxymethyl group at their C2 position with baker's yeast or CBS catalyst.
J Org Chem. 2005 Jun 10;70(12):4652-8. doi: 10.1021/jo050349a.
10
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