Boron-Catalyzed Site-Selective Reduction of Carbohydrate Derivatives with Catecholborane
Boron-Catalyzed Site-Selective Reduction of Carbohydrate Derivatives with Catecholborane
复制标题
DOI：
10.1021/acscatal.8b02337
复制
发表时间：
2018-09-01
期刊：
影响因子：
12.9
通讯作者：
Gagne, Michel R.
中科院分区：
文献类型：
--
作者：
Lowe, Jared M.;Seo, Youngran;Gagne, Michel R.
报道了B（C6 F5）（3）/HBcat催化sp（3）C-O键断裂反应。该方法首先在简单醚和甲硅烷基保护的醇上得到证明，它们表现出与已知的B（C6 F5）（3）/HSiR 3系统平行的反应性。然而，在更复杂的碳水化合物衍生物中，已经实现了使用氢硅烷还原剂不可能实现的独特选择性，包括区域选择性环化。初步的计算研究表明，二硼氧离子是不利的，四配位硼离子可能有助于选择性。
Catalytic sp(3) C-O bond cleavage using B(C6F5)(3)/HBcat is reported. This method is first demonstrated on simple ethers and silyl protected alcohols, which exhibit reactivity parallel to the known B(C6F5)(3)/HSiR3 system. In more complex carbohydrate derivatives, however, unique selectivities that are not possible with hydrosilane reductants have been achieved, including regioselective cyclizations. Preliminary computational studies suggest that diboryl oxonium ions are disfavored and that four-coordinate boronium ions may contribute to selectivity.