Browse > Article
http://dx.doi.org/10.5012/bkcs.2011.32.11.3973

Mechanistic Study of Half-titanocene-based Reductive Pinacol Coupling Reaction  

Kim, Young-Jo (Department of Chemistry, Chungbuk National University)
Do, Young-Kyu (Department of Chemistry, KAIST)
Park, Sung-Jin (Department of Chemistry, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.32, no.11, 2011 , pp. 3973-3978 More about this Journal
Abstract
The reductive pinacol coupling reaction of aldehydes or ketones creating a new C-C bond has been a major tool to produce 1,2-diol compounds. The reaction mechanism is known to be composed of sequential three steps (activation, coupling, and dissociation). In this work, we studied the dissociation step of half-titanocene-based catalytic systems. Cp and $Cp^*$ derivatives of the pinacolato-bridged dinuclear complex were synthesized and evaluated as possible models for intermediates from the coupling step. We monitored $^1H$-NMR spectra of the reaction between the metalla-pinacol intermediates and $D_2O$. New reaction routes of the dissociation step including oxo- and pinacolato-dibridged dinuclear complexes and oxo-bridged multinuclear complexes have been suggested.
Keywords
Reductive coupling reaction; Pinacol; Half-titanocene; Mechanism; NMR;
Citations & Related Records

Times Cited By Web Of Science : 0  (Related Records In Web of Science)
Times Cited By SCOPUS : 0
연도 인용수 순위
  • Reference
1 Sheldrick, G. M. SHELXL-97: Program for the Refinement of Crystal Structures, Universitat Gottingen: Germany, 1997.
2 Corey, E. J.; Danheiser, R. L.; Chandrasekaran, S. J. Org. Chem. 1976, 41, 260.   DOI
3 Kopf, H.; Grabowski, S.; Voigtlander, R. J. Organomet. Chem. 1981, 216, 185.   DOI   ScienceOn
4 Carofiglio, T.; Floriani, C.; Sgamellotti, A.; Rosi, M.; Chiesi- Villa, A.; Rizzoli, C. J. Chem. Soc., Dalton Trans. 1992, 1081.
5 Palacios, F.; Royo, P.; Serrano, R.; Balcazar, J. L.; Fonseca, I.; Florecio, F. J. Organomet. Chem. 1989, 375, 51.   DOI   ScienceOn
6 Gowik, P.; Klapotke, T.; Pickardt, J. J. Organomet. Chem. 1990, 393, 343.   DOI   ScienceOn
7 McMurry, J. E.; Fleming, M. P. J. Am. Chem. Soc. 1974, 96, 4708.   DOI
8 McMurry, J. E. Chem. Rev. 1989, 89, 1513.   DOI
9 Furstner, A.; Bogdanovic, B. Angew. Chem. Int. Ed. Engl. 1996, 35, 2442.   DOI   ScienceOn
10 Clerici, A.; Clerici, L.; Porta, O. Tetrahadron Lett. 1996, 37, 3035.   DOI   ScienceOn
11 Barden, M. C.; Schwartz, J. J. Am. Chem. Soc. 1996, 118, 5484.   DOI   ScienceOn
12 Bandini, M.; Cozzi, P. G.; Morganti, S.; Umani-Ronchi, A. Tetrahedron Lett. 1999, 40, 1997.   DOI   ScienceOn
13 Lipski, T. A.; Hilfiker, M. A.; Nelson, S. G. J. Org. Chem. 1997, 62, 4566.   DOI   ScienceOn
14 Huffman, J. C.; Moloy, K. G.; Marsella, J. A.; Caulton, K. G. J. Am. Chem. Soc. 1980, 102, 3009.   DOI
15 Aleandri, L. E.; Bogdanovic, B.; Gaidies, A.; Jones, D. J.; Liao, S.; Michalowicz, A.; Rozière, J.; Schott, A. J. Organomet. Chem. 1993, 459, 87.   DOI   ScienceOn
16 Aleandri, L. E.; Becke, S.; Bogdanovic, B.; Jones, D. J.; Roziere, J. J. Organomet. Chem. 1994, 472, 97.   DOI   ScienceOn
17 Bogdanovic, B.; Bolte, A. J. Organomet. Chem. 1995, 502, 109.   DOI   ScienceOn
18 Pasquali, M.; Floriani, C.; Chiesi-Villa, A.; Guastini, C. Inorg. Chem. 1981, 20, 349.   DOI
19 Ephritikhine, M.; Maury, O.; Villiers, C.; Lance, M.; Nierlich, M. J. Chem. Soc., Dalton Trans. 1998, 3021.
20 Ephritikhine, M. Chem. Commun. 1998, 2549.
21 Villiers, C.; Ephritikhine, M. Chem. Eur. J. 2001, 7, 3043.   DOI   ScienceOn
22 Furstner, A.; Hupperts, A. J. Am. Chem. Soc. 1995, 117, 4468.   DOI   ScienceOn
23 Souppe, J.; Danon, L.; Namy, J. L.; Kagan, H. B. J. Organomet. Chem. 1983, 250, 227.   DOI   ScienceOn
24 SMART, Version 5.0, Data Collection Software, Bruker AXS, Inc.: Madison, WI, 1998.
25 Balsells, R. E.; Frasca, A. R. Tetrahedron 1982, 38, 245.   DOI   ScienceOn
26 Furstner, A.; Csuk, R.; Rohrer, C.; Weidmann, H. J. Chem. Soc. Perkin Trans. 1988, 1729.
27 Yoon, S. W.; Kim, Y.; Kim, S. K.; Kim, S. Y.; Do, Y.; Park, S. Macromol. Chem. Phys. 2011, 212, 785.   DOI   ScienceOn
28 SAINT, Version 5.0, Data Integration Software, Bruker AXS, Inc.: Madison, WI, 1998.
29 Sheldrick, G. M. SADABS, A Program for Absorption Correction with the Bruker SMART System, Universitat Gottingen: Germany, 1996.
30 Robertson, G. M. Comprehensive Organic Synthesis, Vol 3., Pergamon: Oxford, 1991; pp 563-611.
31 Furstner, A. Angew. Chem. Int. Ed. Engl. 1993, 32, 164.   DOI
32 Wirth, T. Angew. Chem. Int. Ed. Engl. 1996, 35, 61.   DOI
33 Nicolaou, K. C.; Liu, J.-J.; Yang, Z.; Ueno, H.; Sorensen, E. J.; Claiborne, C. F.; Guy, R. K.; Hwang, C.-K.; Nakada, M.; Nantermet, P. G. J. Am. Chem. Soc. 1995, 117, 634.   DOI   ScienceOn
34 Mukaiyama, T.; Sato, T.; Hanna, J. Chem. Lett. 1973, 1041.
35 Tyrlik, S.; Wolochowicz, I. Bull. Soc. Chim. Fr. 1973, 2147.