Synthesis and structures of gold and copper carbene intermediates in catalytic amination of alkynes

• Published in: Nature communications 2017-03, Vol.8 (1), p.14625-14625, Article 14625
• Main Authors: Wang, Jiwei, Cao, Xiaoming, Lv, Shichang, Zhang, Caiyun, Xu, Sheng, Shi, Min, Zhang, Jun
• Format: Article
• Language: English
• Subjects: 140/131; 639/638/263/406; 639/638/403/934; 639/638/77/885; Catalysis; Copper; Decomposition; Gold; Humanities and Social Sciences; multidisciplinary; Oxidation; Science; Science (multidisciplinary)
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/ncomms14625

Metal carbenes are often proposed as reactive intermediates in the late transition metal-catalysed transformations of alkynes. Owing to their high reactivity, however, isolation and structural characterization of metal carbene intermediates in these transformations has remained unknown. Herein, we report the isolation of two acyclic gold and copper carbene intermediates in either Au(I)- or Cu(I)-catalysed cyclization of N -alkynyl formamidines through five- exo -dig cyclization. X-ray diffraction, 13 C NMR spectra data and computational analyses provide evidence for the formation of a gold carbene intermediate with a carbocation-like electronic character. Using the intrinsic bond orbital (IBO) approach, we also evaluate the π-stabilizing effects of organic substituents at the carbene carbon atom in the gold carbene intermediate. Another rare six-membered copper carbene complex is also obtained through 6- endo -dig cyclization. These metal carbenes have proven reactive toward oxidation. The metal-promoted cyclization of N -alkynyl formamidine provides a facile approach to synthesize metal carbene species. Metal carbenes are typically highly reactive and unstable species, proposed as intermediates in numerous catalytic processes. Here the authors report the isolation and characterization of gold and copper carbene intermediates involved in catalytic cyclization reactions.