The Bipodal Compounds [(TMG2biphenN-R)CuI-NCMe](PF6) (R = Me, Ar (4-CF3Ph-)) And [(TMG2biphenN-Me)CuI-I] Have Been Synthesized With Ligands That Feature A Diarylmethyl- And Triaryl-Amine Framework And Superbasic Tetramethylguanidinyl Residues (TMG). The Cationic Cu(I) Sites Mediate Catalytic Nitrene-Transfer Reactions Between The Imidoiodinane PhI = NTs (Ts = Tosyl) And A Panel Of Styrenes In MeCN, To Afford Aziridines, Demonstrating Comparable Reactivity Profiles. The Copper Reagents Have Been Further Explored To Execute C-H Amination Reactions With A Variety Of Aliphatic And Aromatic Hydrocarbons And Two Distinct Nitrene Sources PhI = NTs And PhI = NTces (Tces = 2,2,2-Trichloroethylsulfamate) In Benzene/HFIP (10:2 V/v). Good Yields Have Been Obtained For Sec-Benzylic And Tert-C-H Bonds Of Various Substrates, Especially With The More Electron-Deficient Catalyst [(TMG2biphenN-Ar)CuI-NCMe](PF6). In Conjunction With Earlier Studies, The Order Of Reactivity Of These Bipodal Cationic Reagents As A Function Of The Metal Employed Is Established As Cu > Fe > Co ≥ Mn. However, As Opposed To The Base-Metal Analogues, The Bipodal Cu Reagents Are Less Reactive Than A Similar Tripodal Cu Catalyst. The Observed Fluorophilicity Of The Bipodal Cu Compounds May Provide A Deactivation Pathway.



Publication Status

Open Access

International Standard Serial Number (ISSN)


Document Type

Article - Journal

Document Version

Final Version

File Type





© 2024 American Chemical Society, All rights reserved.

Creative Commons Licensing

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 License.

Publication Date

01 Jan 2024