Pyridine-bridged bis-benzimidazolylidene nickel complexes exhibited very high catalytic activity toward cross coupling of inactive(hetero)aryl benzylic ammonium salts with(hetero)aryl and alkenyl boronic acids und...Pyridine-bridged bis-benzimidazolylidene nickel complexes exhibited very high catalytic activity toward cross coupling of inactive(hetero)aryl benzylic ammonium salts with(hetero)aryl and alkenyl boronic acids under mild reaction conditions.Even at 2 mol% catalyst loading,a wide range of substrates for both coupling partners with different steric and electronic properties were well tolerated.展开更多
The sustainable development of synthetic reactions catalyzed by earth-abundant metals is one of the principal goals in homogeneous catalysis.However,so far most of the protocols are still plagued by sophisticated liga...The sustainable development of synthetic reactions catalyzed by earth-abundant metals is one of the principal goals in homogeneous catalysis.However,so far most of the protocols are still plagued by sophisticated ligands,hazardous activators,high catalyst loading(1—10 mol%)and/or multistep synthesis of the metal complexes in the process development.Consequently,the development of earth-abundant metal catalysts with high activity from commercially available metal salts is highly desirable for practical utilization of base metal catalyzed synthetic methodology.Herein,we report the catalyst generated in situ from a mixture of catalytic amounts of Ni(acac)_(2)(as low as 0.005 mol%)and CsF,which is found highly active for Markovnikov-selective hydroboration of vinylarenes,including 1,1-disubstituted vinylarenes and internal olefins,affording a wide range of secondary and tertiary alkyl boronates in excellent yields.Mechanistic experiments indicate that the key to the success of this catalysis is the use of CsF,which in combination with pinacolborane acts as an effective activator for Ni(acac)_(2),probably generating metastable Ni nanoparticles in situ that demonstrate high activity in the catalytic hydroboration(TON up to 18800).展开更多
基金the National Natural Science Foundation of China (Nos. 21572036, 21172045 and 91127041)the Changjiang Scholars and Innovative Research Team in University (No. IRT-15R12)+2 种基金the Shanghai International Cooperation Program (No. 14230710600)the Doctoral Fund of Ministry of Education of China (No. 20130071110032)Department of Chemistry Fudan University
文摘Pyridine-bridged bis-benzimidazolylidene nickel complexes exhibited very high catalytic activity toward cross coupling of inactive(hetero)aryl benzylic ammonium salts with(hetero)aryl and alkenyl boronic acids under mild reaction conditions.Even at 2 mol% catalyst loading,a wide range of substrates for both coupling partners with different steric and electronic properties were well tolerated.
基金The authors acknowledge financial support from the National Natural Science Foundation of China(No.21821002).
文摘The sustainable development of synthetic reactions catalyzed by earth-abundant metals is one of the principal goals in homogeneous catalysis.However,so far most of the protocols are still plagued by sophisticated ligands,hazardous activators,high catalyst loading(1—10 mol%)and/or multistep synthesis of the metal complexes in the process development.Consequently,the development of earth-abundant metal catalysts with high activity from commercially available metal salts is highly desirable for practical utilization of base metal catalyzed synthetic methodology.Herein,we report the catalyst generated in situ from a mixture of catalytic amounts of Ni(acac)_(2)(as low as 0.005 mol%)and CsF,which is found highly active for Markovnikov-selective hydroboration of vinylarenes,including 1,1-disubstituted vinylarenes and internal olefins,affording a wide range of secondary and tertiary alkyl boronates in excellent yields.Mechanistic experiments indicate that the key to the success of this catalysis is the use of CsF,which in combination with pinacolborane acts as an effective activator for Ni(acac)_(2),probably generating metastable Ni nanoparticles in situ that demonstrate high activity in the catalytic hydroboration(TON up to 18800).