Year: 2025
Type: preprint
Abstract: We report an enantioselective 1,2 arylamination of unactivated alkenes catalyzed by a chiral indenyl Rh(III) complex, using Troc protected hydroxylamine derivatives. This method enables efficient access to structurally diverse 2 aminotetralin scaffolds and amino substituted carbospirocycles via a 6 endo cyclization involving electrophilic aromatic substitution (EAS). Experimental and computational studies reveal that the electronic asymmetry of the chiral indenyl ligand plays a pivotal role in enhancing catalytic activity compared to cyclopentadienyl based analogs. Furthermore, the identity of the N protecting group on hydroxylamine significantly influences the reaction pathway, distinguishing this transformation from previously reported aziridination strategies. The synthetic utility and versatility of this catalytic system are further demonstrated through streamlined syntheses of biologically relevant molecules, highlighting its strong potential for applications in medicinal chemistry.
Source: ChemRxiv
Authors: Patrick Gross, Hyoju Choi, Wesley Pullara, Hoyoung Im, Harry Ung, Seunguk Kang, Mu-Hyun Baik, Simon Blakey
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Awards: OCE-PRF Track 1: Biological Mercury Hotspots: The Role of Phytoplankton Blooms in Nearshore Marine Mercury Bioaccumulation, G1933497434, Innovation in Catalyst and Oxidative Amination Reaction Development for the Synthesis of Darobactin and Other Ribosomally Synthesized Post-translationally Modified Peptides (RiPPs)
OpenAlex ID: W4415493985