Mechanism for reduction catalysis by metal oxo: Hydrosilation of organic carbonyl groups catalyzed by a rhenium(V) oxo complex

Journal of the American Chemical Society

Volumn 127, Issue 44, 2005, Pages 15374-15375

  Ison, Elon A ^a   Trivedi, Evan R ^a   Corbin, Rex A ^a   Abu Omar, Mahdi M ^a  

^a PURDUE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; CARBONYL DERIVATIVE; KETONE DERIVATIVE; METAL OXIDE; RHENIUM COMPLEX; SILANE DERIVATIVE;

ARTICLE; CATALYSIS; CATALYST; HYDROSILYLATION; OXIDATION; PRECIPITATION; REACTION ANALYSIS; REDUCTION;

EID: 27644553194     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja055704t     Document Type: Article

References (25)

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2. (b) Nugent, W. A.; Mayer, J. M. Metal-Ligand Multiple Bonds; Wiley: New York, 1988.
3. (c) Handbook of Reagents for Organic Synthesis: Oxidizing and Reducing Agents; Burke, S. D., Danheiser, R. L., Eds.; John Wiley & Sons: New York, 1999.
4. Recent examples of metal-catalyzed hydrosilation: (a) Yun, J.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 5640 (Ti catalyst),
5. (b) Reyes, C.; Prock, A.; Giering, W. P. Organometallics 2002, 21, 546 (Rh/BINAP catalyst),
6. (c) For a review on hydrosilation, see: Ojima, I.; Li, Z.; Zhu, J. In The Chemistry of Organic Silicon Compounds; Rappoport, Z., Apelog, Y., Eds.; John Wiley & Sons: New York, 1998.
7. 2 catalyst: Kennedy-Smith, J. J.; Nolin, K. A.; Gunterman, H. P.; Toste, F. D. J. Am. Chem. Soc. 2003, 125, 4056.
8. 2 catalyst: Fernandes, A. C.; Fernandes, R.; Romao, C. C.; Royo, B. Chem. Commun. 2005, 213.
9. 7, oxorhenium catalysts reported require heating at 80 °C and 5 mol % catalyst loading,
10. v(O) catalyst for reduction of imines: Nolin, K. A.; Ahn, R. W.; Toste, F. D. J. Am. Chem. Soc. 2005, 127, 12462.
11. Thiel, W. R. Angew. Chem., Int. Ed. 2003, 42, 5390.
12. + does not catalyze the hydrosilation reaction.
13. See Supporting Information for details. (7) (a) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87, 16.
14. (b) Chaloner, P. A.; Esteruelas, M. A.; Jou, F.; Oro, L. A. Homogeneous Hydrogenation; Kluwer Academic: Boston, 1994.
15. 7, fail to catalyze the hydrosilation reaction and are stable in boiling water (i.e., not hydridic). See ref 3a.
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22. 2 (see Figures S4 and S5).
23. 3SiH to give ethylbenzene and regenerate the silylium catalyst. For our system, we do not detect any ethylbenzene in the NMR.
24. + followed by carbonyl group addition in a [3 + 2] mechanism is also possible. However, the observed KIE is closer in value to that observed for σ-bond metathesis. See, for example: Sadow, A. D., Tilley, T. D. J. Am. Chem. Soc. 2005, 127, 643.
25. 2-silane complexes, see: Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789.