Research Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan Lu, Shanghai, 200433, P. R. China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, P. R. China.
Angew Chem Int Ed Engl. 2022 Nov 21;61(47):e202211635. doi: 10.1002/anie.202211635. Epub 2022 Oct 21.
Rh-catalyzed dynamic kinetic intramolecular [4+2] cycloaddition reaction of 1,3-disubstituted allene-1,3-dienes afforded cis-fused [4.3.0]bicyclic products with an excellent chemo-, diastereo-, and enantio-selectivity. Many synthetically useful functional groups are tolerated. The synthetic utility has been demonstrated. Based on the careful experimental studies, a mechanism involving the rapid racemization of the allene moiety in the starting materials has been proposed.
铑催化的 1,3-二取代丙二烯-1,3-二烯的动态动力学分子内[4+2]环加成反应以优异的化学选择性、非对映选择性和对映选择性提供顺式稠合[4.3.0]双环产物。许多合成上有用的官能团都可以耐受。合成的实用性已经得到了证明。基于仔细的实验研究，提出了一种涉及起始物料中丙二烯部分快速外消旋化的机制。
