Fast "Wittig-like" reactions as a consequence of the inorganic enamine effect.
作者： Stella A. Gonsales , Matias E. Pascualini , Ion Ghiviriga , Khalil A. Abboud , Adam S. Veige
DOI: 10.1021/JACS.5B01599
关键词:
摘要: The tungsten alkylidyne [CF3–ONO]W≡CC(CH3)3(THF)2 (3) {where CF3–ONO = (MeC6H3[C(CF3)2O])2N3–} supported by a trianionic pincer-type ligand demonstrates enhanced nucleophilicity in unusually fast “Wittig-like” reactions. Experiments are designed to provide support for an inorganic enamine effect that is the origin of nucleophilicity. Treating complex 3 with various carbonyl-containing substrates provides tungsten-oxo-vinyl complexes upon oxygen atom transfer. rates reactivity compared known (DIPP)3W≡CC(CH3)3 (DIPP 2,6-diisopropylphenoxide). In all cases (except acetone), exhibits significantly faster overall than (DIPP)3W≡CC(CH3)3. New oxo-vinyl characterized NMR, combustion analysis and single crystal X-ray diffraction. acid chlorides oxo chloride species [CF3–ONO]W(O)Cl (4) disubstituted alkynes. case acetone results two rotational isomers 10syn...
acs.org
sci-hub.se 参考文章(29)
John H. Freudenberger, Richard R. Schrock, Multiple metal-carbon bonds. 41. Wittig-like reactions of tungsten alkylidyne complexes Organometallics. ,vol. 5, pp. 398- 400 ,(1986) , 10.1021/OM00133A041
Rüdiger Beckhaus, Cristina Santamarı́a, Carbene complexes of titanium group metals — formation and reactivity Journal of Organometallic Chemistry. ,vol. 617, pp. 81- 97 ,(2001) , 10.1016/S0022-328X(00)00710-5
Marco G. Crestani, Anne K. Hickey, Xinfeng Gao, Balazs Pinter, Vincent N. Cavaliere, Jun-Ichi Ito, Chun-Hsing Chen, Daniel J. Mindiola, Room Temperature Dehydrogenation of Ethane, Propane, Linear Alkanes C4–C8, and Some Cyclic Alkanes by Titanium–Carbon Multiple Bonds Journal of the American Chemical Society. ,vol. 135, pp. 14754- 14767 ,(2013) , 10.1021/JA4060178
Brad C. Bailey, Hongjun Fan, John C. Huffman, Mu-Hyun Baik, Daniel J. Mindiola, Intermolecular C−H Bond Activation Reactions Promoted by Transient Titanium Alkylidynes. Synthesis, Reactivity, Kinetic, and Theoretical Studies of the Ti⋮C Linkage Journal of the American Chemical Society. ,vol. 129, pp. 8781- 8793 ,(2007) , 10.1021/JA070989Q
Matthew E. O'Reilly, Ion Ghiviriga, Khalil A. Abboud, Adam S. Veige, Unusually stable tungstenacyclobutadienes featuring an ONO trianionic pincer-type ligand. Dalton Transactions. ,vol. 42, pp. 3326- 3336 ,(2013) , 10.1039/C2DT32653A
Brian T. Connell, Thomas A. Kirkland, Robert H. Grubbs, Conversion of Acid Chlorides to Substituted Acetylenes with Tungsten Alkylidynes Organometallics. ,vol. 24, pp. 4684- 4686 ,(2005) , 10.1021/OM050352K
Guillermo C. Bazan, Richard R. Schrock, Marie B. O'Regan, Synthesis and kinetics of decomposition of tungsten(VI) and molybdenum(VI) 2-oxametallacyclobutane complexes and the x-ray structure of trans-Mo[CH(tert-Bu)CH(C6F5)O](NAr)(O-tert-Bu)2 Organometallics. ,vol. 10, pp. 1062- 1067 ,(1991) , 10.1021/OM00050A043
Richard C. Hartley, Gordon J. McKiernan, Titanium reagents for the alkylidenation of carboxylic acid and carbonic acid derivatives Journal of The Chemical Society-perkin Transactions 1. pp. 2763- 2793 ,(2002) , 10.1039/B009709H
Richard R. Schrock, Alkylcarbene complex of tantalum by intramolecular .alpha.-hydrogen abstraction Journal of the American Chemical Society. ,vol. 96, pp. 6796- 6797 ,(1974) , 10.1021/JA00828A061
Soumya Sarkar, Khalil A. Abboud, Adam S. Veige, Addition of Mild Electrophiles to a Mo≡N Triple Bond and Nitrile Synthesis via Metal-Mediated N-Atom Transfer to Acid Chlorides Journal of the American Chemical Society. ,vol. 130, pp. 16128- 16129 ,(2008) , 10.1021/JA805629X