Department of Chemistry , University of Chicago , Chicago , Illinois 60637 , United States.
Department of Chemistry , University of Pittsburgh , Pittsburgh , Pennsylvania 15260 , United States.
J Am Chem Soc. 2019 Oct 16;141(41):16260-16265. doi: 10.1021/jacs.9b09344. Epub 2019 Oct 2.
Herein we describe the development of a highly selective kinetic resolution of cyclobutanones via a Rh-catalyzed "cut-and-sew" reaction with selectivity factor up to 785. This reaction takes place at room temperature with excellent efficiency. Various -5,6-fused bicycles and C2-substituted cyclobutanones were obtained with excellent ee's that can be further used as chiral building blocks. DFT calculations reveal the crucial roles of the DTBM-segphos ligand in stabilizing the rate- and enantioselectivity-determining C-C oxidative addition transition state via favorable ligand-substrate dispersion interactions.
在这里,我们描述了通过 Rh 催化的“切缝”反应对环丁酮进行高对映选择性动力学拆分的发展,该反应的选择性因子高达 785。该反应在室温下进行,具有优异的效率。各种 -5,6-稠合的自行车和 C2-取代的环丁酮以优异的对映选择性ee 值获得,可以进一步用作手性砌块。DFT 计算揭示了 DTBM-segphos 配体在通过有利的配体-底物分散相互作用稳定速率和对映选择性决定的 C-C 氧化加成过渡态方面的关键作用。