Abstract
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.
Recommended Citation
S. K. Sahoo et al., "A Comparative Study Of Cationic Copper(I) Reagents Supported By Bipodal Tetramethylguanidinyl-Containing Ligands As Nitrene-Transfer Catalysts," ACS Omega, American Chemical Society, Jan 2024.
The definitive version is available at https://doi.org/10.1021/acsomega.4c00909
Department(s)
Chemistry
Publication Status
Open Access
International Standard Serial Number (ISSN)
2470-1343
Document Type
Article - Journal
Document Version
Final Version
File Type
text
Language(s)
English
Rights
© 2024 American Chemical Society, All rights reserved.
Creative Commons Licensing
This work is licensed under a Creative Commons Attribution 4.0 License.
Publication Date
01 Jan 2024
