Synthesis of amino-diamondoid pharmacophores via photocatalytic C–H aminoalkylation

Abstract

We report a direct C–H aminoalkylation reaction using two light-activated H-atom transfer catalyst systems that enable the introduction of protected amines to native adamantane scaffolds with C–C bond formation. The...

α-Chiral Amines via Thermally Promoted Deaminative Addition of Alkylpyridinium Salts to Sulfinimines

“…Tin-mediated activation of alkyl iodides has demonstrated these to be competent alkyl radical precursors . Redox-active esters have also been used with both photoredox and nickel catalysis. , …”

Synergistic Brønsted/Lewis acid catalyzed aromatic alkylation with unactivated tertiary alcohols or di-tert-butylperoxide to synthesize quaternary carbon centers

“…Alkylation of phenol (1) occurred selectively at the para position, affording 3aa–3ad in 71–85% yields. Adamantane is a privileged structure that has earned the reputation of being a “lipophilic bullet” for enhancing pharmacological activity 34 and various methods have been devised for their derivatization, 35 including a Friedel–Crafts strategy that requires trifluoroacetic acid as the solvent. 36 Here, dual FeCl 3 /HCl catalysis allows arylation of 1-adamantanol under mild reaction conditions.…”

Synthesis of Chiral Amines by C–C Bond Formation with Photoredox Catalysis

“…Martin recently developed a photoredox-catalyzed Hatom transfer method to generate radicals from adamantanes in a route to amino-diamondoid pharmacophores. 90 Using the Ir catalyst [Ir{dF(CF 3 )ppy} 2 {d(CF 3 )bpy}]PF 6 (4.26) in combination with quinuclidine co-catalyst 4.27 (Scheme 44), C-H activation of adamantane derivatives and their re-ductive radical addition to various benzaldehyde N-tosylimines and N-benzoylhydrazones gave adducts 4.28. Cyclic N-sulfonylimines were also successful in this reaction.…”