51-73-0Relevant articles and documents
Preparation of Tremorine and Gemini Surfactant Precursors with Cationic Ethynyl-Bridged Digold Catalysts
Grirrane, Abdessamad,álvarez, Eleuterio,García, Hermenegildo,Corma, Avelino
, p. 2792 - 2801 (2017/03/06)
Tremorine and precursors of gemini surfactants were synthesised in a one-pot, three-step, double-catalytic A3coupling reaction and characterised by structural and spectroscopic methods. The cationic [AuI(L1)]SbF6complex is a more active catalyst compared to neutral L2– and L3–AuIbis(trifluoromethanesulfonyl)imidate complexes (L1, L2=Buchwald-type biaryl phosphane; L3=triphenylphosphine) in promoting the double A3coupling of ethynyltrimethylsilane, secondary amines (cyclic, aliphatic, or aromatic) and formaldehyde. The solvent influences the catalytic performance by desilylation of silyl acetylene or deactivation of the catalyst by a halide anion. Acetylide-bridged cationic digold(I) L1 and L2 complexes were isolated and characterised by means of single-crystal X-ray structure analysis and their spectroscopic properties. Iodine in the acetylene reagent deactivates the AuIcatalyst by formation of the less active iodido-bridged cationic digold(I) L1 complex, which was fully characterised by single-crystal X-ray crystal structure analysis and spectroscopy. The nature of the phosphine ligand of the gold complexes used as catalyst affects the stability and activity of the formed cationic ethynyl-bridged AuI2–L intermediates, isolation of which lends support to the proposed double A3coupling mechanism.
N-Propargylation of secondary amines directly using calcium carbide as an acetylene source
Fu, Rugang,Li, Zheng
, p. 341 - 345 (2017/06/19)
A one-pot N-propargylation of secondary amines has been achieved by heating the amine with formaldehyde and calcium carbide in DMSO in the presence of CuCl as a catalyst. Fifteen examples of propargylic tertiary amines, 12 of which are novel, were efficiently prepared in yields of 65-84%. The advantages of the method are broad substrate scope and a simple work-up procedure.