Alkynophilicity of Group 13 MX3 Salts: A Theoretical Study.
作者： Vincent Gandon , Vincent Gandon , Christophe Bour , Shengwen Yang , Shengwen Yang
DOI: 10.1021/ACS.INORGCHEM.0C03302
关键词: Metal salts 、 Dissociation (chemistry) 、 Medicinal chemistry 、 Carbocation 、 Group (periodic table) 、 Reactivity (chemistry) 、 Monomer 、 Ligand 、 Chemistry
摘要: The concept of alkynophilicity is revisited with group 13 MX3 metal salts (M = In, Ga, Al, B; X Cl, OTf) using M06-2X/6-31+G(d,p) calculations. This study aims at answering why some these show reactivity toward enynes that similar to observed late-transition-metal complexes, notably Au(I) species, and them are inactive. For this purpose, the mechanism skeletal reorganization 1,6-enynes into 1-vinylcyclopentenes has been computed, including monomeric ("standard") dimeric (superelectrophilic) activation. Those results confronted deactivation pathways based on dissociation M-X bond. role ligand in stabilization intermediate nonclassical carbocation revealed, whole features required make a good π-Lewis acid discussed.
acs.org
sci-hub.st 参考文章(92)
M. Mori, T. Kitamura, 11.08 – Ene–Yne and Alkyne Metathesis Comprehensive Organometallic Chemistry III#R##N#From Fundamentals to Applications. ,vol. 11, pp. 271- 310 ,(2007) , 10.1016/B0-08-045047-4/00152-7
P. Jeffrey Hay, Willard R. Wadt, Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals Journal of Chemical Physics. ,vol. 82, pp. 299- 310 ,(1985) , 10.1063/1.448975
Yoshinori Yamamoto, From σ- to π-Electrophilic Lewis Acids. Application to Selective Organic Transformations Journal of Organic Chemistry. ,vol. 72, pp. 7817- 7831 ,(2007) , 10.1021/JO070579K
H. P. Hratchian, H. B. Schlegel, Using Hessian Updating To Increase the Efficiency of a Hessian Based Predictor-Corrector Reaction Path Following Method. Journal of Chemical Theory and Computation. ,vol. 1, pp. 61- 69 ,(2005) , 10.1021/CT0499783
Corinne Aubert, Olivier Buisine, Max Malacria, The behavior of 1,n-enynes in the presence of transition metals. Chemical Reviews. ,vol. 102, pp. 813- 834 ,(2002) , 10.1021/CR980054F
Dinesh V. Vidhani, John W. Cran, Marie E. Krafft, Mariappan Manoharan, Igor V. Alabugin, Gold(I)-catalyzed Claisen rearrangement of allenyl vinyl ethers: missing transition states revealed through evolution of aromaticity, Au(I) as an oxophilic Lewis acid, and lower energy barriers from a high energy complex. Journal of Organic Chemistry. ,vol. 78, pp. 2059- 2073 ,(2013) , 10.1021/JO302152J
Felipe de Jesus Cortez, Richmond Sarpong, Ga(III)-Catalyzed Cycloisomerization Approach to (±)-Icetexone and (±)-Epi-Icetexone Organic Letters. ,vol. 12, pp. 1428- 1431 ,(2010) , 10.1021/OL902959V
Kenichi Fukui, The path of chemical reactions - the IRC approach Accounts of Chemical Research. ,vol. 14, pp. 363- 368 ,(1981) , 10.1021/AR00072A001
Zbyněk Černý, Jiří Macháček, Jiří Fusek, Bohuslav Čásenský, Otomar Křīž, Dennis G. Tuck, Multinuclear NMR studies of mixtures of aluminium and gallium trihalides in benzene Journal of The Chemical Society-dalton Transactions. pp. 2698- 2703 ,(2001) , 10.1039/B102483N
Angela Marinetti, Hélène Jullien, Arnaud Voituriez, Enantioselective, transition metal catalyzed cycloisomerizations. Chemical Society Reviews. ,vol. 41, pp. 4884- 4908 ,(2012) , 10.1039/C2CS35020C