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 Jun 27;61(26):e202203661. doi: 10.1002/anie.202203661. Epub 2022 May 3.
The enantioselective cascade reaction between racemic 2-(1-hydroxyallyl)phenols and alkynols/alkynamides was realized by using a gold and iridium sequential catalytic system. In this procedure, the in situ generated exocyclic vinyl ethers or enamides undergo the asymmetric allylation/spiroketalization with π-ally-Ir amphiphilic species, which provides an efficient and straightforward access to spiroketals and spiroaminals with excellent enantioselectivities. Moreover, racemic 2-(1-hydroxyallyl)anilines were also suitable in this reaction along with a kinetic resolution process, affording enantioenriched spiroaminals and 2-(1-hydroxyallyl)anilines in good yields. The synthetic utility of this method has been demonstrated by efficient enantioselective synthesis of the analogue of Paecilospirone.
通过使用金和铱顺序催化体系，实现了外消旋 2-(1-羟烯丙基)苯酚与炔醇/炔酰胺之间的对映选择性级联反应。在该步骤中，原位生成的环外乙烯基醚或烯胺与π-烯丙基-Ir 两亲性物种进行不对称烯丙基化/螺缩酮化反应，为具有优异对映选择性的螺缩酮和螺环亚胺提供了有效且直接的途径。此外，外消旋 2-(1-羟烯丙基)苯胺也适用于该反应，并通过动力学拆分过程，以良好的收率得到对映体富集的螺环亚胺和 2-(1-羟烯丙基)苯胺。该方法的合成实用性已通过 Paecilospirone 类似物的高效对映选择性合成得到证明。
