Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai 980-8578, Japan.
Org Lett. 2022 Jan 28;24(3):960-965. doi: 10.1021/acs.orglett.1c04331. Epub 2022 Jan 14.
Direct and diastereoselective synthesis of vicinal -,-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 ()-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.
锌介导的醛与环丙醇的α-羟烯丙基化反应实现了邻位-，-二醇的直接和立体选择性合成。该反应的特点是锌烯醇化的偕烯醇盐作为γ-氧烯丙基亲核试剂作用于羰基亲电试剂。本反应的立体选择性归因于烯醇化偕烯醇盐螯合（）-构型的强烈偏好以及它与醛形成的双环椅式过渡态，其中醛取代基倾向于占据假轴向位置。
