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Chiral Osmium(II)/Salox Species Enabled Enantioselective γ-C(sp 3 )-H Amidation: Integrated Experimental and Computational Validation For the Ligand Design and Reaction Development.

Weijie ChenHuiying XuFu-Xiaomin LiuKaifeng ChenZhi ZhouWei Yi
Published in: Angewandte Chemie (International ed. in English) (2024)
Herein, multiple types of chiral Os(II) complexes have been designed to address the appealing yet challenging asymmetric C(sp 3 )-H functionalization, among which the Os(II)/Salox species is found to be the most efficient for precise stereocontrol in realizing the asymmetric C(sp 3 )-H amidation. As exemplified by the enantioenriched pyrrolidinone synthesis, such tailored Os(II)/Salox catalyst efficiently enables an intramolecular site-/enantioselective C(sp 3 )-H amidation in the γ-position of dioxazolone substrates, in which benzyl, propargyl and allyl groups bearing various substituted forms are well compatible, affording the corresponding chiral γ-lactam products with good er values (up to 99 : 1) and diverse functionality (>35 examples). The unique performance advantage of the developed chiral Os(II)/Salox system in terms of the catalytic energy profile and the chiral induction has been further clarified by integrated experimental and computational studies.
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