Selective Gold‐Catalysed Synthesis of Cyanamides and 1‐Substituted 1H‐Tetrazol‐5‐Amines from Isocyanides

Abstract

The newly discovered gold-catalysed reaction of isocyanides with hydrazoic acid generated in situ from trimethylsilyl azide and methanol (or, alternatively, from NaN /AcOH) produces either cyanamides or 1-substituted 1H-tetrazol-5-amines, depending on the amount of available HN . The reaction proceeds selectively and in generally high yields of either product, thus providing a particularly convenient access to a wide range of substituted 1H-tetrazol-5-amines that are rather difficult to access otherwise.

A more sustainable and highly practicable synthesis of aliphatic isocyanides

“…11 and 13). While the new synthesis for the compounds 10 and 12 was more sustainable in terms of the E-factor compared to the literature procedures (62.0-24.9/28.9-14.7), 61,62 this is not the case for compound 11, yet the yields were comparable (22.2 to 25.6). 9 In 2013, for example, Kim et al published a convenient synthesis protocol for isocyanides in a continuous-flow microreactor with excellent yields for 10 and 11.…”

Protic Ferrocenyl Acyclic Diamino Carbene Gold(I) Complexes

“…[similar to a literature procedure for (1'-(diphenylphosphino)-1-isocyanoferrocene)(AuCl) 2 ]. [115,116] 200 mg (0.68 mmol, 1 eq) of chlorido(dimethyl sulfide)gold(I) was dissolved in CH 2 Cl 2 (15 mL). Isocyanoferrocene (143.3 mg, 0.68 mmol, 1 eq) was added as solid and the solution was stirred for 10-15 minutes.…”

An Environmentally Benign, Catalyst‐Free N−C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides

“…Ethyl 4‐formamidobenzoate [20c] ( 3 t ): Using the experimental procedure EP‐1 , the product was obtained as white solid in 72 % yield. A mixture of rotamers is observed; 1 H NMR (400 MHz, DMSO‐d 6 ) δ 10.53 (Major rotamer, s, 0.73H), 10.46 (Minor rotamer, d, J =10.7 Hz, 0.25H), 8.96 (Minor rotamer, d, J =10.7 Hz, 0.24H), 8.35 (Major rotamer, s, 0.75H), 7.91 (t, J =10.5 Hz, 2.01H), 7.71 (d, J =8.5 Hz, 1.53H), 7.31 (t, J =7.6 Hz, 0.61H), 4.28 (q, J =7.1 Hz, 2H), 1.30 (t, J =7.1 Hz, 3H); 13 C NMR (100 MHz, DMSO‐d 6 ) δ Major rotamer: 160.11, 142.43, 130.32, 118.62, minor rotamer: 162.53, 142.90, 121.19, 116.43.…”