Journal
SCIENCE CHINA-CHEMISTRY
Volume 63, Issue 2, Pages 215-221Publisher
SCIENCE PRESS
DOI: 10.1007/s11426-019-9601-7
Keywords
palladium-arene interaction; hydrogenative desymmetrization; 1; 3-diketones
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Funding
- National Natural Science Foundation of China [21871255, 21532006, 21873096]
- Chinese Academy of Sciences [XDB17020300, XDB17010200]
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For the metal-catalyzed asymmetric hydrogenation of alpha-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 beta-hydroxy ketones with two adjacent stereocenters including one alpha-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.
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