Synthesis 2018; 50(22): 4462-4470
DOI: 10.1055/s-0037-1609858
paper
© Georg Thieme Verlag Stuttgart · New York

Site-Selective, Catalyst-Controlled Alkene Aziridination

Amirah S. Mat Lani
Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison WI 53706, USA   Email: schomakerj@chem.wisc.edu
,
Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison WI 53706, USA   Email: schomakerj@chem.wisc.edu
› Author Affiliations
This work was funded by NSF Award 1664374 and the Wisconsin Alumni Research Foundation to J.M.S. The NMR facilities at UW-Madison are funded by the NSF (CHE-9208463, CHE-9629688) and NIH (RR08389-01). The National Magnetic Resonance Facility at Madison is supported by the NIH (P41GM103399, S10RR08438 and S10RR029220) and the NSF (BIR-0214394). The purchase of the Thermo Q Exactive™ Plus in 2015 for mass spectrometry was funded by NIH Award 1S10 OD020022-1 to the Department of Chemistry.
Further Information

Publication History

Received: 05 April 2018

Accepted after revision: 27 April 2018

Publication Date:
23 July 2018 (eFirst)

Abstract

Transition-metal-catalyzed nitrene transfer is a convenient method to introduce nitrogen into simple substrates through either alkene aziridination or C–H bond amination. Silver complexes have an unusual capability to accommodate a broad range of N-donor ligands and coordination geometries in catalysts competent for nitrene transfer. This behavior has resulted in the ability to achieve tunable chemoselectivity between aziridination and C–H bond amidation, as well as tunable site-selective functionalization between two different C–H bonds. In this paper, efforts to engage the diversity of silver and rhodium catalysts to accomplish selective and tunable aziridination of mixtures of alkenes are discussed. It was found that the selectivity of dinuclear Rh catalysts is dictated largely by steric effects, while the identity of the ligand on silver can be tuned to influence whether the steric or electronic features in the competing alkenes is the primary factor controlling which precursor is preferentially aziridinated.

Supporting Information

 
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