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A Catalytic Dual Isomerization/Allylboration Sequence for the Stereoselective Construction of Congested Secondary Homoallylic Alcohols
The Journal of Organic Chemistry ( IF 3.6 ) Pub Date : 2020-03-26 , DOI: 10.1021/acs.joc.0c00565
Yangbin Liu 1 , Clément Mazet 1
Affiliation  

A catalytic sequence for the diastereo- and enantioselective preparation of homoallylic alcohols with an adjacent quaternary (stereo)center is reported. The one-pot process relies on the use of a single (achiral or chiral) iridium complex to catalyze the concomitant isomerization of primary allylic alcohols and homoallylboronates into (chiral) aldehydes and allylboronates, respectively. In the same flask, a chiral Brønsted acid is added next to engage the isomerization products into a stereocontrolled allylboration reaction. Structural variations have been performed on both the allylic alcohols and the homoallylboronates. This mild process affords an array of stereochemically congested and complex chiral secondary homoallylic alcohols in high yield, excellent diastereoselectivity, and usually high enantioselectivity.

中文翻译:

催化的二级异构化/烯丙基硼化序列的拥挤的二级均烯丙基醇的立体选择性构建。

报道了具有相邻的季(立体)中心的均烯丙基醇的非对映和对映选择性制备的催化序列。一锅法依赖于使用单个(非手性或手性)铱配合物来催化伯烯丙基醇和高烯丙基硼酸酯的同时异构化为(手性)醛和烯丙基硼酸酯。在同一烧瓶中,接着添加手性布朗斯台德酸,使异构化产物参与立体可控的烯丙基硼化反应。已经对烯丙基醇和高烯丙基硼酸酯进行了结构变化。这种温和的过程以高收率,优异的非对映选择性和通常较高的对映选择性提供了一系列立体化学富集和复杂的手性仲均烯丙基醇。
更新日期:2020-04-24
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