Copper(I)-Catalyzed Dehydrative C-Glycosidation of Unprotected Pyranoses with Ketones
Copper(I)-Catalyzed Dehydrative C-Glycosidation of Unprotected Pyranoses with Ketones
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DOI：
10.1021/acscatal.6b02106
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发表时间：
2016-09
期刊：
影响因子：
12.9
通讯作者：
Xiao-Feng Wei;Shi‐Liang Shi;Xiao-Wei Xie;Yohei Shimizu;M. Kanai
中科院分区：
文献类型：
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作者：
Xiao-Feng Wei;Shi‐Liang Shi;Xiao-Wei Xie;Yohei Shimizu;M. Kanai
我们开发了一种铜（I）催化的酮非对映选择性掺入到未保护的吡喃糖。的反应性是依赖于在铜催化剂的双膦配体的咬角，我们确定了一个非手性双膦配体L1轴承作为最佳配体的一个非常大的咬角。含配体L1的铜（I）共轭布朗斯台德碱催化剂能够通过原位生成的烯醇化铜（I）实现C-C键形成反应，即使在多个未保护的羟基存在下也是如此。以高的非对映选择性引入了多种酮。产物2，6-顺式-吡喃在生物活性分子的合成中具有许多应用。
We developed a copper(I)-catalyzed diastereoselective incorporation of ketones into unprotected pyranoses. The reactivity was dependent on the bite angle of the diphosphine ligand in the copper catalyst, and we identified an achiral diphosphine ligand L1 bearing an exceptionally large bite angle as the optimal ligand. A copper(I)-conjugated Brϕnsted base catalyst containing ligand L1 enabled the C–C bond-forming reaction via in situ-generated copper(I) enolate, even in the presence of multiple unprotected hydroxy groups. A variety of ketones were introduced with high diastereoselectivity. The product 2,6-cis-pyrans has many applications for the synthesis of biologically active molecules.