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

Jiwei Wang, Xiaoming Cao, Shichang Lv, Caiyun Zhang, Sheng Xu, Min Shi and Jun Zhang ()
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Jiwei Wang: Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology
Xiaoming Cao: Center for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry & Molecular Engineering, East China University of Science and Technology
Shichang Lv: Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology
Caiyun Zhang: Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology
Sheng Xu: Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology
Min Shi: Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology
Jun Zhang: Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology

Nature Communications, 2017, vol. 8, issue 1, 1-10

Abstract: Abstract 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, 13C 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.

Date: 2017
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DOI: 10.1038/ncomms14625

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