Fig. 4: Chemical transformation of the cyanamide functionality.
From: Iron-catalysed radical Markovnikov hydroamidation of complex alkenes
a, Different reactions of the cyanamide functionality either at the NH moiety or at the nitrile group. The free amine 7 can also be obtained through hydrolysis of the urea 8 with DETA at 140 °C for 12 h (93% yield). b, N-arylation through cooperative photoredox/nickel catalysis. c, Cu-catalysed N-benzylation. d, Intramolecular N-alkylation at elevated temperature under basic conditions. e, N-benzylation followed by Ir-catalysed cycloaddition for pyridine construction. f, N-aroylation and subsequent radical cascade cyclization. Reactions were carried out on 0.1 mmol scale, and all yields provided refer to isolated yields. TMS, trimethylsilyl; Bz, benzoyl; THF, tetrahydrofuran; 4CzIPN, 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene; TMG, tetramethylguanidine; DMA, dimethylacetamide; LED, light-emitting diode; DMF, dimethylformamide; cod, 1,5-cyclooctadiene; DPPF, 1,1′-bis(diphenylphosphino)ferrocene; ppy, 2-phenylpyridine; DIPEA, diisopropylethylamine.
