Syntheses of asymmetrical magnesium(I) complexes and their catalytic application in epoxide hydroboration
作者： Xu Cao , Jia Li , Anqiao Zhu , Fan Su , Weiwei Yao
DOI: 10.1039/D0QO00938E
关键词: Alkyl 、 Hydroboration 、 Reaction mechanism 、 Magnesium 、 Aryl 、 Epoxide 、 Markovnikov's rule 、 Chemistry 、 Polymer chemistry 、 Catalysis
摘要: A series of asymmetrical β-diketiminate ligand stabilized magnesium(I) complexes have been successfully synthesized and structurally characterized via single crystal X-ray diffraction. When they were employed as efficient catalysts in the hydroboration aryl, alkyl alicyl epoxides with pinacolborane (HBpin), resultant borate ester products obtained high yields regioselectivities. The results also revealed that showed a marked preference for branched Markovnikov hydroborated instead linear anti-Markovnikov esters which are typically formed protocols involving transition metal catalysts. preliminary reaction mechanism has investigated corresponding DFT calculation.
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sci-hub.st 参考文章(37)
Sinji Murai, Toshiaki Murai, Shinzi Kato, Reduction of Epoxides Comprehensive Organic Synthesis. ,vol. 4, pp. 871- 893 ,(1991) , 10.1016/B978-0-08-052349-1.00249-3
Cameron Jones, Andreas Stasch, Stable Molecular Magnesium(I) Dimers: A Fundamentally Appealing Yet Synthetically Versatile Compound Class ChemInform. ,vol. 46, pp. 73- 101 ,(2013) , 10.1007/978-3-642-36270-5_3
Catherine Weetman, Mathew D. Anker, Merle Arrowsmith, Michael S. Hill, Gabriele Kociok-Köhn, David J. Liptrot, Mary F. Mahon, Magnesium-catalysed nitrile hydroboration Chemical Science. ,vol. 7, pp. 628- 641 ,(2016) , 10.1039/C5SC03114A
S. P. Green, C. Jones, A. Stasch, Stable Magnesium(I) Compounds with Mg-Mg Bonds Science. ,vol. 318, pp. 1754- 1757 ,(2007) , 10.1126/SCIENCE.1150856
Jacques Muzart, Pd‐Mediated Reactions of Epoxides European Journal of Organic Chemistry. ,vol. 2011, pp. 4717- 4741 ,(2011) , 10.1002/EJOC.201100143
Che Chang Chong, Rei Kinjo, Catalytic Hydroboration of Carbonyl Derivatives, Imines, and Carbon Dioxide ACS Catalysis. ,vol. 5, pp. 3238- 3259 ,(2015) , 10.1021/ACSCATAL.5B00428
Simon J. Bonyhady, Cameron Jones, Sharanappa Nembenna, Andreas Stasch, Alison J. Edwards, Garry J. McIntyre, β-Diketiminate-Stabilized Magnesium(I) Dimers and Magnesium(II) Hydride Complexes: Synthesis, Characterization, Adduct Formation, and Reactivity Studies Chemistry: A European Journal. ,vol. 16, pp. 938- 955 ,(2010) , 10.1002/CHEM.200902425
Shaun P. Green, Cameron Jones, Andreas Stasch, Stable Adducts of a Dimeric Magnesium(I) Compound Angewandte Chemie. ,vol. 47, pp. 9079- 9083 ,(2008) , 10.1002/ANIE.200803960
Merle Arrowsmith, Terrance J. Hadlington, Michael S. Hill, Gabriele Kociok-Köhn, Magnesium-catalysed hydroboration of aldehydes and ketones Chemical Communications. ,vol. 48, pp. 4567- 4569 ,(2012) , 10.1039/C2CC30565H
S. Florio, F.M Perna, A. Salomone, P. Vitale, 8.29 Reduction of Epoxides Reference Module in Chemistry, Molecular Sciences and Chemical Engineering#R##N#Comprehensive Organic Synthesis II (Second Edition). pp. 1086- 1122 ,(2014) , 10.1016/B978-0-08-097742-3.00831-4