Reversal of diastereoselectivity in palladium-arene interaction directed hydrogenative desymmetrization of 1,3-diketones

• 来源期刊: 中国科学:化学（英文版）
• 年，卷（期）: 2020,（2）
• 页码范围: 215-221
• 页数: 7页
• 语种: 英文

摘要

For the metal-catalyzed asymmetric hydrogenation of α-substituted ketones,cis reductive products are generally obtained due to steric hindrance of substituents.Herein,an unprecedented trans reductive products were observed in palladium-catalyzed hydrogenative desymmetrization of cyclic and acyclic 1,3-diketones,providing the chiral trans β-hydroxy ketones with two adjacent stereocenters including one a-tertiary or quaternary stereocenter with high enantioselectivity and diastereoselectivity.Mechanistic studies and DFT calculations suggested that the rarely observed diastereoselectivity reversal is ascribed to the charge-charge interaction between the palladium and aromatic ring of the substrate,which could not only result in the reversal of the diastereoselectivity,but also improve the reactivity.