葡糖醛 3-氨基甲酸酯氨基糖苷化反应中立体和化学选择性的保护基团及溶剂控制
Protecting group and solvent control of stereo- and chemoselectivity in glucal 3-carbamate amidoglycosylation.
作者信息
Gupta Ritu, Sogi Kimberly M, Bernard Sarah E, Decatur John D, Rojas Christian M
机构信息
Department of Chemistry, Barnard College, 3009 Broadway, New York, New York 10027, USA.
出版信息
Org Lett. 2009 Apr 2;11(7):1527-30. doi: 10.1021/ol900126q.
Abstract
In the Rh(2)(OAc)(4)-catalyzed amidoglycosylation of glucal 3-carbamates, anomeric stereoselectivity and the extent of competing C3-H oxidation depend on the 4O and 6O protecting groups. Acyclic protection permits high alpha-anomer selectivity with further improvement in less polar solvents, while electron-withdrawing protecting groups limit C3-oxidized byproducts. Stereocontrol and bifurcation between alkene insertion and C3-H oxidation reflect an interplay of conformational, stereoelectronic, and inductive factors.
摘要
在Rh(2)(OAc)(4)催化的3-氨基甲酸酯基葡糖醛的氨糖基化反应中，端基立体选择性和C3-H氧化竞争程度取决于4-O和6-O保护基。无环保护允许高α-端基异构体选择性，在极性较小的溶剂中进一步改善，而吸电子保护基限制C3-氧化副产物。烯烃插入和C3-H氧化之间的立体控制和分支反映了构象、立体电子和诱导因素的相互作用。
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