Stereodefined Access to Lactams via Olefin Difunctionalization: Iridium Nitrenoids as a Motif of LUMO-Controlled Dipoles

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Title
Stereodefined Access to Lactams via Olefin Difunctionalization: Iridium Nitrenoids as a Motif of LUMO-Controlled Dipoles
Author(s)
Seung Youn Hong; Sukbok Chang
Publication Date
2019-07
Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.141, no.26, pp.10399 - 10408
Publisher
AMER CHEMICAL SOC
Abstract
© 2019 American Chemical Society.Reported herein is a general platform of a stereodefined access to γ-lactams via Cp∗Ir-catalyzed olefin difunctionalization, where in situ generated Ir-nitrenoid is utilized as a key motif of 1,3-dipoles to enable amido transfer in a syn-selective manner. Computational studies suggested that the stereodefined process can be attributed to the proposed working mode of concerted [3 + 2] cyclization. Frontier molecular orbital (FMO) analysis implied that a low-lying lowest unoccupied molecular orbital (LUMO) of the Ir-imido fragment engages in the olefin interaction. Mechanistic understanding on the nitrene transfer process led us to develop mild catalytic protocols of stereoselective difunctionalization of alkenyl dioxazolones to furnish α-(haloalkyl)- or (oxyalkyl)lactam products which are of high synthetic and medicinal utility. Product stereochemistry (threo and erythro) was found to be designated by the olefin geometry (E/Z) of substrates
URI
https://pr.ibs.re.kr/handle/8788114/6061
ISSN
0002-7863
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
Files in This Item:
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