Palladium-Catalyzed Enantioselective 7-<i>exo</i>-Trig Carbopalladation/Carbonylation: Cascade Reactions To Achieve Atropisomeric Dibenzo[<i>b</i>,<i>d</i>]azepin-6-ones
Huaanzi Hu, Yan Peng, Ting Yu, Sidi Cheng, Shuang Luo, Qiang Zhu
Abstract
Enantioselective 7-exo-trig cyclocarbopalladation-initiated carbonylation cascade reactions, leading to seven-membered dibenzo[b,d]azepin-6-ones containing a thermodynamically controlled stereogenic axis, have been realized for the first time. A series of 7-acetate- or 7-acetamide-substituted dibenzo[b,d]azepin-6-ones are obtained under atmospheric pressure of CO in good yields with excellent diastereo- and enantioselectivities. The calculated energy difference between the diastereoisomers generated from the stereogenic biaryl axis and the stereogenic center is approximately 2.8 kcal/mol, which agrees with the excellent diastereoselectivity observed.
Topics & Concepts
StereocenterChemistryCarbonylationEnantioselective synthesisDiastereomerCatalysisAcetamideStereochemistryPalladiumCascadeMedicinal chemistryOrganic chemistryChromatographyCarbon monoxideAxial and Atropisomeric Chirality SynthesisCatalytic C–H Functionalization MethodsMolecular spectroscopy and chirality