Intramolecular endo-dig hydrosilylation catalyzed by ruthenium: Evidence for a new mechanistic pathway

Journal of the American Chemical Society

Volumn 125, Issue 1, 2003, Pages 30-31

  Trost, Barry M ^a   Ball, Zachary T ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; ALKENE; ALKYNE; CHEMICAL COMPOUND; DICHLOROMETHANE; GAMMA HYDROXY KETONE; HOMOPROPARGYLIC ALCOHOL; KETONE; LEWIS ACID; MAGNESIUM TRISILICATE; PLATINUM; RUTHENIUM; SILICON; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL REACTION; GEOMETRY; HYDROGEN BOND; HYDROSILYLATION; ISOMERISM; OXIDATION; STEREOCHEMISTRY;

ALKYNES; CATALYSIS; CYCLIZATION; ORGANOMETALLIC COMPOUNDS; RUTHENIUM; SILANES; VINYL COMPOUNDS;

EID: 0037425510     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja028766h     Document Type: Article

References (21)

1. Molander, G. A.; Retsch, W. H. Organometallics 1995, 14, 4570-4575; Ojima, I.; Li, Z.; Zhu, J. In The Chemistry of Organosilicon Compounds; Rappoport, Z., Apeloig, Y., Eds.; John Wiley & Sons: Great Britain, 1998; Vol. 2, pp 1687-1792.
2. Molander, G. A.; Retsch, W. H. Organometallics 1995, 14, 4570-4575; Ojima, I.; Li, Z.; Zhu, J. In The Chemistry of Organosilicon Compounds; Rappoport, Z., Apeloig, Y., Eds.; John Wiley & Sons: Great Britain, 1998; Vol. 2, pp 1687-1792.
3. Trost, B. M.; Ball, Z. T. J. Am. Chem. Soc. 2001, 123, 12726-12727.
4. Denmark, S. E.; Pan, W. T. Org. Lett. 2001, 3, 61-64.
5. Marshall, J. A.; Yanik, M. M. Org. Lett. 2000, 2, 2173-2175.
6. Tamao, K.; Maeda, K.; Tanaka, T.; Ito, Y. Tetrahedron Lett. 1988, 29, 6955-6956.
7. After the submission of this manuscript, an example of such exo-dig hydrosilylation to afford a deriviative of -3 using a different ruthenium catalyst has appeared: Denmark, S. E.; Pan, W. Org. Lett. 2002, 4, 4163-4166.
8. Sudo, T.; Asao, N.; Yamamoto, Y. J. Org. Chem. 2000, 65, 8919-8923.
9. Tamao, K.; Ishida, N.; Tanaka, T.; Kumada, M. Organometallics 1983, 2, 1694-1696.
10. Jun, C. H.; Crabtree, R. H. J. Organomet. Chem. 1993, 447, 177-187; Ojima. I.; Clos, N.; Donovan, R. J.; Ingallina, P. Organometallics 1990, 9, 3127-3133; Faller, J. W.; D'Alliessi, D. G. Organometallics 2002, 21, 1743-1746.
11. Jun, C. H.; Crabtree, R. H. J. Organomet. Chem. 1993, 447, 177-187; Ojima. I.; Clos, N.; Donovan, R. J.; Ingallina, P. Organometallics 1990, 9, 3127-3133; Faller, J. W.; D'Alliessi, D. G. Organometallics 2002, 21, 1743-1746.
12. Jun, C. H.; Crabtree, R. H. J. Organomet. Chem. 1993, 447, 177-187; Ojima. I.; Clos, N.; Donovan, R. J.; Ingallina, P. Organometallics 1990, 9, 3127-3133; Faller, J. W.; D'Alliessi, D. G. Organometallics 2002, 21, 1743-1746.
13. Addition products analyzed by GC-MS. The trans stereochemistry of addition for terminal alkynes has been established in a related experiment. See Supporting Information.
14. Although the conversion of 13 to 14 can be envisioned, the absence of any products derived from reductive elimination of the intermediates, together with the lack of an obvious thermodynamic driving force for these interconversions make such a route difficult to accept.
15. It is also possible that direct trans addition is facilitated by a dinuclear ruthenium complex, provided that only one silane molecule is involved. For a recent report with evidence of a trans hydrometalation with a dinuclear ruthenium complex, see: Martin, M.; Sola, E.; Lahoz, F. J.; Oro, L. A. Organometallics 2002, 21, 4027-4029. However, our evidence precludes the involvement of species such as those presented therin.
16. Tanaka, K.; Fu, G. C. J. Am. Chem. Soc. 2001, 123, 11492-11493; Tanaka, K.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 1607-1609.
17. Tanaka, K.; Fu, G. C. J. Am. Chem. Soc. 2001, 123, 11492-11493; Tanaka, K.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 1607-1609.
18. Kawanami, Y.; Sonoda, Y.; Mori, T.; Yamamoto, K. Org. Lett. 2002, 4, 2825-2827; Na, Y.; Chang, S. Org. Lett. 2000, 2, 1887-1889; Esteruelas, M. A.; Herrero, J.; Oro, L. A. Organometallics 1993, 12, 2377-2379; Katayama, H.; Taniguchi, K.; Kobayashi, M.; Sagawa, T.; Minami, T.; Ozawa, F. J. Organomet. Chem. 2002, 645, 192-200.
19. Kawanami, Y.; Sonoda, Y.; Mori, T.; Yamamoto, K. Org. Lett. 2002, 4, 2825-2827; Na, Y.; Chang, S. Org. Lett. 2000, 2, 1887-1889; Esteruelas, M. A.; Herrero, J.; Oro, L. A. Organometallics 1993, 12, 2377-2379; Katayama, H.; Taniguchi, K.; Kobayashi, M.; Sagawa, T.; Minami, T.; Ozawa, F. J. Organomet. Chem. 2002, 645, 192-200.
20. Kawanami, Y.; Sonoda, Y.; Mori, T.; Yamamoto, K. Org. Lett. 2002, 4, 2825-2827; Na, Y.; Chang, S. Org. Lett. 2000, 2, 1887-1889; Esteruelas, M. A.; Herrero, J.; Oro, L. A. Organometallics 1993, 12, 2377-2379; Katayama, H.; Taniguchi, K.; Kobayashi, M.; Sagawa, T.; Minami, T.; Ozawa, F. J. Organomet. Chem. 2002, 645, 192-200.
21. Kawanami, Y.; Sonoda, Y.; Mori, T.; Yamamoto, K. Org. Lett. 2002, 4, 2825-2827; Na, Y.; Chang, S. Org. Lett. 2000, 2, 1887-1889; Esteruelas, M. A.; Herrero, J.; Oro, L. A. Organometallics 1993, 12, 2377-2379; Katayama, H.; Taniguchi, K.; Kobayashi, M.; Sagawa, T.; Minami, T.; Ozawa, F. J. Organomet. Chem. 2002, 645, 192-200.