Monocoordinating, compact phosphane immobilized on silica surface: Application to rhodium-catalyzed hydrosilylation of hindered ketones

Angewandte Chemie - International Edition

Volumn 46, Issue 28, 2007, Pages 5381-5383

  Hamasaka, Go ^a   Ochida, Atsuko ^a   Hara, Kenji ^a   Sawamura, Masaya ^a  

^a HOKKAIDO UNIVERSITY   (Japan)

Author keywords

Hydrosilylation; Immobilization; Phosphanes; Phosphorus heterocycles; Rhodium

Indexed keywords

BUTYLDIMETHYLSILYL; COORDINATION BEHAVIOR; PHOSPHORUS HETEROCYCLES;

CATALYSIS; COORDINATION REACTIONS; HYDROSILYLATION; PHOSPHATES; RHODIUM COMPOUNDS; SURFACE CHEMISTRY;

SILICA;

EID: 34447573862     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200700947     Document Type: Article

References (16)

1. 2 group was tenfold higher than those with the longer-chain analogues: a) M. Czaková, M. Čapka, J. Mol. Catal. 1981, 11, 313;
2. b) Z. M. Michalska, M. Čapka, J. Stoch, J. Mol. Catal. 1981, 11, 323.
3. For a related study, in which a bulky phosphane attached to a rigid polymer support was used for the Suzuki-Miyaura coupling, see: Q.-S. Hu, Y. Lu, Z.-Y. Tang, H.-B. Yu, J. Am. Chem. Soc. 2003, 125, 2856.
4. SMAP = silicon-constrained monodentate alkylphosphane. a) A. Ochida, K. Hara, H. Ito, M. Sawamura, Org. Lett. 2003, 5, 2671;
5. b) A. Ochida, S. Ito, T. Miyahara, H. Ito, M. Sawamura, Chem. Lett. 2006, 35, 294.
6. 29Si CP/MAS NMR spectrum.
7. a) O. Niyomura, M. Tokunaga, Y. Obora, T. Iwasawa, Y. Tsuji, Angew. Chem. 2003, 115, 1325;
8. Angew. Chem. Int. Ed. 2003, 42, 1287;
9. b) O. Niyomura, T. Iwasawa, N. Sawada, M. Tokunaga, Y. Obora, Y. Tsuji, Organometallics 2005, 24, 3468;
10. see also: c) A. Ochida, M. Sawamura, Chem. Asian J., 2007, 2, 609;
11. d) H. Ito, T. Kato, M. Sawamura, Chem. Lett. 2006, 35, 1038.
12. 2SiH, but their reactivity toward highly hindered ketones has not extensively been studied: B. H. Lipshutz, C. C. Caires, P. Kuipers, W. Chrisman, Org. Lett. 2003, 5, 3085.
13. 2SiH, has yet to be demonstrated: a) S. Díez-González, H. Kaur, F. K. Zinn, E. D. Stevens, S. P. Nolan, J. Org. Chem. 2005, 70, 4784;
14. b) S. Díez-González, N. M. Scott, S. P. Nolan, Organometallics 2006, 25, 2355.
15. DFT calculations of the P-donor power of MeO-SMAP, a model compound for 1, indicated that the electronic effect of the support is negligible; see reference [3a].
16. 2(smap)]. This catalyst precursor should release the two ethylene ligands upon rapid hydrosilylation prior to entering a catalytic cycle. [silica]-[RhCl(cod)(smap)] can also be used but needs to be aged with a hydrosilane before the addition of a ketone.