Abstract
The mechanism of an asymmetric ring-opening (ARO) addition of oxabicyclic alkenes catalyzed by a platinum(ii) catalyst was investigated by M06-2X/6-311G(d,p) using density functional theory (DFT). All the structures were optimized in the solvent model density (SMD) solvation model (solvation = the mixture of H2O/CH2Cl2 1 : 10, v/v) for consistence with experimental conditions. The overall mechanism is considered as a four-step reaction including transmetalation, carboplatinum, β-oxygen elimination, and hydrolysis. The transmetalation and carboplatinum steps are multi-step processes, and both the regioselectivity and the enantioselectivity lie in the carboplatinum process. Based on the natural population analysis (NPA) and the orbital composition analysis of oxabicyclic alkenes, the preferable coordination site with a platinum(ii) center is considered as the bridging oxygen atom by exo-coordination because of the less steric hindrance and the stronger electronic effect. This coordination is thought of as origin of the regioselectivity and the enantioselectivity, which is different from that proposed previously. The Gibbs free energy profiles show that the rate-determining step involves the migration of an aryl group from the pla...Continue Reading
References
Jul 13, 2000·Organic Letters·M LautensJ L Renaud
Apr 13, 2002·Organic Letters·Mark LautensAdrianna Malicki
Dec 5, 2003·Organic Letters·Dinesh Kumar RayabarapuChien-Hong Cheng
Feb 5, 2004·Journal of the American Chemical Society·Mark Lautens, Sheldon Hiebert
Apr 3, 2004·The Journal of Organic Chemistry·Paul Leong, Mark Lautens
Apr 7, 2004·Proceedings of the National Academy of Sciences of the United States of America·Mark Lautens, Keith Fagnou
Jun 23, 2005·Journal of the American Chemical Society·Ataualpa A C BragaFeliu Maseras
Aug 25, 2005·Journal of the American Chemical Society·Tsuneo ImamotoKazuhiro Yoshida
Nov 25, 2005·Journal of the American Chemical Society·Silvia CabreraJuan C Carretero
Mar 16, 2006·Journal of the American Chemical Society·Karine Villeneuve, William Tam
Jan 16, 2008·The Journal of Organic Chemistry·Alphonse Tenaglia, Sylvain Marc
Aug 8, 2008·Organic Letters·Ting-Ke ZhangXue-Long Hou
Oct 23, 2008·Organic Letters·Masahiro YoshidaKozo Shishido
Apr 16, 2009·The Journal of Physical Chemistry. B·Aleksandr V MarenichDonald G Truhlar
Oct 2, 2009·Organic Letters·Yoshinari SawamaNorbert Krause
Jan 26, 2011·Organic Letters·Kohei EndoTakanori Shibata
Mar 12, 2011·Angewandte Chemie·Thierry AchardGérard Buono
Dec 14, 2011·Journal of Computational Chemistry·Tian Lu, Feiwu Chen
Jan 5, 2012·Chemical Communications : Chem Comm·Pieter H BosBen L Feringa
Feb 14, 2013·The Journal of Physical Chemistry. a·Yu ChangR Bruce King
Nov 28, 2013·The Journal of Organic Chemistry·Xuejing PanDingqiao Yang
Feb 14, 2015·The Journal of Organic Chemistry·Ling MengDingqiao Yang
Jan 12, 2017·Scientific Reports·Zheng-Hang QiYong Wang
Jan 18, 2017·Journal of the American Chemical Society·Abing DuanK N Houk