A facile and practical synthetic route of unsymmetrical 1,3-diynes via the PdC1/CuI catalyzed oxidative coupling of two different terminal alkynes has been developed by using 3-（diphenylphosphino）propanoic acid as a...A facile and practical synthetic route of unsymmetrical 1,3-diynes via the PdC1/CuI catalyzed oxidative coupling of two different terminal alkynes has been developed by using 3-（diphenylphosphino）propanoic acid as a ligand in the presence of oxygen. This system is suitable for not only aromatic alkynes but also heteroaromatic and aliphatic alkynes which were transformed into the corresponding unsymmetrical 1,3-diynes in moderate to good yields at room temperature. Moreover, the unsymmetrical 1,3-diynes were also obtained on a multi-gram scale. Mechanistic studies suggest that oxygen plays a key role in the catalytic cycles.展开更多
O_(x)idative couplings of aliphatic alkynes are crucial for the production of naturally occurring 1,3-diynes.Herein we report the novel approach for effective synthesis of unsaturated coordinated N doped copper oxides...O_(x)idative couplings of aliphatic alkynes are crucial for the production of naturally occurring 1,3-diynes.Herein we report the novel approach for effective synthesis of unsaturated coordinated N doped copper oxides(N-CuO_(x))catalyst,and uncover that N-CuO_(x) catalyst as an additive-free and cost-effective heterogeneous catalyst has highly catalytic performance for directly oxidative coupling of aliphatic alkynes.The key to achieve efficient oxidative coupling of aliphatic alkynes is the synergistic effect of N species and uncoordinated O/Cu species caused by N dopants,which undergoes the Langmuir–Hinshelwood reaction mechanism.The N-CuO_(x) catalyst displays~89.1%yield for hexadeca-7,9-diyne under mild conditions and stable reusability(5 cycles),showing significant advances compared with the traditionally copper oxides.These findings highlight the heteroatom dopants that provide a new methodology for designing efficient copper catalysts in synthesis of naturally occurring 1,3-diynes.展开更多
基金We gratefully acknowledge the financial support of this work by the National Natural Science Foundation of China （Nos. 21563025, 21463022）, Shihezi University Training Programme for Distinguished Youth Scholars （No. 2014ZRKXJQ05）, and Start-Up Foundation for Young Scientists of Shihezi University （No. RCZX201408）.
文摘A facile and practical synthetic route of unsymmetrical 1,3-diynes via the PdC1/CuI catalyzed oxidative coupling of two different terminal alkynes has been developed by using 3-（diphenylphosphino）propanoic acid as a ligand in the presence of oxygen. This system is suitable for not only aromatic alkynes but also heteroaromatic and aliphatic alkynes which were transformed into the corresponding unsymmetrical 1,3-diynes in moderate to good yields at room temperature. Moreover, the unsymmetrical 1,3-diynes were also obtained on a multi-gram scale. Mechanistic studies suggest that oxygen plays a key role in the catalytic cycles.
基金supported by the“Key Program for International S&T Cooperation Projects of China”(No.2017YFE0124300)Anhui Provincial Natural Science Foundation of China(No.2008085M47)+1 种基金Key Projects of the Department of Education of Anhui Province of China(No.RZ2000003450)The authors thank the beamline BL14W1 at Shanghai Synchrotron Radiation Facility(SSRF).
文摘O_(x)idative couplings of aliphatic alkynes are crucial for the production of naturally occurring 1,3-diynes.Herein we report the novel approach for effective synthesis of unsaturated coordinated N doped copper oxides(N-CuO_(x))catalyst,and uncover that N-CuO_(x) catalyst as an additive-free and cost-effective heterogeneous catalyst has highly catalytic performance for directly oxidative coupling of aliphatic alkynes.The key to achieve efficient oxidative coupling of aliphatic alkynes is the synergistic effect of N species and uncoordinated O/Cu species caused by N dopants,which undergoes the Langmuir–Hinshelwood reaction mechanism.The N-CuO_(x) catalyst displays~89.1%yield for hexadeca-7,9-diyne under mild conditions and stable reusability(5 cycles),showing significant advances compared with the traditionally copper oxides.These findings highlight the heteroatom dopants that provide a new methodology for designing efficient copper catalysts in synthesis of naturally occurring 1,3-diynes.
