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Silylative Reductive Amination of α,β‐Unsaturated Aldehydes: A Convenient Synthetic Route to β‐Silylated Secondary Amines
Chemistry - A European Journal ( IF 4.3 ) Pub Date : 2018-03-25 , DOI: 10.1002/chem.201800958
Eunae Kim 1, 2, 3 , Sehoon Park 1, 2 , Sukbok Chang 1, 2
Affiliation  

Described here is a reductive amination/hydrosilylation cascade of α,β‐unsaturated aldehydes mediated by a Lewis acidic borane catalyst. The present reaction system provides an one‐pot synthetic route towards β‐silylated secondary amines that have not been accessible by other previous catalysis. Comparative 1H NMR studies on the silylative reduction of enimines revealed that steric bulkiness of primary amine reactants strongly affects both catalytic efficiency and regioselectivity. This strategy was applicable to a broad range of substrates and amenable to one‐pot gram‐scale synthesis. Moreover, a diastereoselective introduction of the β‐silyl group was also found to be feasible (d.r. up to 71:29).

中文翻译:

α,β-不饱和醛的甲硅烷基化还原胺化反应:合成β-甲硅烷基化仲胺的简便方法

这里描述的是路易斯酸性硼烷催化剂介导的α,β-不饱和醛的还原胺化/氢化硅烷化级联。本反应系统提供了一种单罐合成路线,可通往其他先前催化无法达到的β-甲硅烷基化仲胺。对亚胺的甲硅烷基化还原进行的比较1 H NMR研究表明,伯胺反应物的空间体积极大地影响了催化效率和区域选择性。该策略适用于广泛的底物,并适用于一锅克级合成。此外,还发现非对映选择性地引入β-甲硅烷基是可行的(dr高达71:29)。
更新日期:2018-03-25
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