Publications
Detailed Information
Stereodefined Access to Lactams via Olefin Difunctionalization: Iridium Nitrenoids as a Motif of LUMO-Controlled Dipoles
Cited 33 time in
Web of Science
Cited 32 time in Scopus
- Authors
- Issue Date
- 2019-07
- Publisher
- American Chemical Society
- Citation
- Journal of the American Chemical Society, Vol.141 No.26, pp.10399-10408
- Abstract
- Reported herein is a general platform of a stereodefined access to gamma-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 alpha-(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.
- ISSN
- 0002-7863
- Files in This Item:
- There are no files associated with this item.
- Appears in Collections:
Item View & Download Count
Items in S-Space are protected by copyright, with all rights reserved, unless otherwise indicated.