Zinc-Mediated Hydroxyallylation of Aldehydes with Cyclopropanols: Direct Access to Vicinal <i>anti</i>-<i>sec</i>,<i>tert</i>-Diols via Enolized Homoenolates
Zinc-Mediated Hydroxyallylation of Aldehydes with Cyclopropanols: Direct Access to Vicinal <i>anti</i>-<i>sec</i>,<i>tert</i>-Diols via Enolized Homoenolates
复制标题
锌介导的醛与环丙醇的羟烯丙基化：通过烯醇化高烯醇化物直接获得邻位<i>抗</i>-<i>仲</i>,<i>叔</i>-二醇
DOI：
10.1021/acs.orglett.1c04331
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发表时间：
2022
期刊：
影响因子：
5.2
通讯作者：
Yoshikai Naohiko
中科院分区：
文献类型：
--
作者：
Sekiguchi Yoshiya;Yoshikai Naohiko
通过锌催化的醛与环丙醇的α-羟烯丙基化反应，实现了芳香族抗仲叔二醇的直接和非对映选择性合成。该反应的特点是锌烯醇化的高烯醇酸作为γ-羟基烯丙基亲核试剂对羰基亲电试剂的作用。反应的非对映选择性归因于烯醇化的高烯醇酸的(Z)-螯合构型的强烈偏好以及它与醛形成的双环椅子状过渡态，其中醛取代基更倾向于占据假轴位置。
Direct and diastereoselective synthesis of vicinalanti-sec,tert-diols has been achieved by zinc-mediated α-hydroxyallylation of aldehydes with cyclopropanols. The reaction features the action of the zinc-enolized homoenolate as a γ-oxyallyl nucleophile toward the carbonyl electrophile. The diastereoselectivity of the present reaction is ascribed to the strong preference for a chelated (Z)-configuration of the enolized homoenolate as well as the bicyclic chairlike transition state it forms with the aldehyde, where the aldehyde substituent prefers to occupy the pseudoaxial position.