Zhang Jian, Yang Wu-Lin, Zheng Hanliang, Wang Yi, Deng Wei-Ping
Shanghai Key Laboratory of Chemical Biology & School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, P. R. China.
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, Jinhua, 321004, P. R. China.
Angew Chem Int Ed Engl. 2022 May 2;61(19):e202117079. doi: 10.1002/anie.202117079. Epub 2022 Mar 10.
An unprecedented asymmetric γ-allylic alkylation of free dienolates via Sc/Ir dual catalysis is reported, which affords a range of synthetically versatile γ-allylic crotonaldehydes in high efficiency with excellent chemo-, regio-, and enantioselectivities. The dienolates bearing no essential auxiliary groups were generated in situ by scandium triflate-mediated Meinwald rearrangement of vinyloxiranes atom-economically. With the assistance of computational density functional theory calculations, a Sc/Ir bimetallic catalytic cycle was proposed to illustrate the reaction mechanism.
报道了一种通过钪/铱双催化实现的前所未有的游离烯醇盐不对称γ-烯丙基烷基化反应，该反应能高效地提供一系列具有合成多功能性的γ-烯丙基巴豆醛，具有优异的化学、区域和对映选择性。通过三氟甲磺酸钪介导的乙烯基环氧乙烷的Meinwald重排，原子经济地原位生成了不含必需辅助基团的烯醇盐。在计算密度泛函理论计算的辅助下，提出了一个钪/铱双金属催化循环来阐明反应机理。
