247118-11-2Relevant academic research and scientific papers
Contra-thermodynamic Hydrogen Atom Abstraction in the Selective C-H Functionalization of Trialkylamine N-CH3 Groups
Barham, Joshua P.,John, Matthew P.,Murphy, John A.
supporting information, p. 15482 - 15487 (2016/12/09)
We report a simple one-pot protocol that affords functionalization of N-CH3 groups in N-methyl-N,N-dialkylamines with high selectivity over N-CH2R or N-CHR2 groups. The radical cation DABCO+?, prepared in situ by oxidation of DABCO with a triarylaminium salt, effects highly selective and contra-thermodynamic C-H abstraction from N-CH3 groups. The intermediates that result react in situ with organometallic nucleophiles in a single pot, affording novel and highly selective homologation of N-CH3 groups. Chemoselectivity, scalability, and recyclability of reagents are demonstrated, and a mechanistic proposal is corroborated by computational and experimental results. The utility of the transformation is demonstrated in the late-stage site-selective functionalization of natural products and pharmaceuticals, allowing rapid derivatization for investigation of structure-activity relationships.
Triarylaminium salt induced oxidative cyclizations of tertiary amines. Convenient access to 2-substituted pyrrolidinium salts
Jahn, Ullrich,Aussieker, Susanne
, p. 849 - 852 (2008/02/09)
(equation presented) Although they are common intermediates, the application of aliphatic tertiary aminium radical cations to organic synthesis has so far been restricted to α-deprotonation and related reactions. We report the very convenient oxidative ge
