Practical method for asymmetric addition of arylboronic acids to α,β-unsaturated carbonyl compounds utilizing an in situ prepared rhodium catalyst

Journal of Organic Chemistry

Volumn 74, Issue 2, 2009, Pages 929-931

  Lukin, Kirill ^a   Zhang, Qunying ^a   Leanna, M Robert ^a  

^a ABBOTT LABORATORIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ARYLBORONIC ACIDS; ASYMMETRIC ADDITIONS; BORONIC ACIDS; IN-SITU; MICHAEL ADDITIONS; PRACTICAL METHODS; RHODIUM CATALYSTS; SUBSTANTIAL REDUCTIONS; UNSATURATED CARBONYL COMPOUNDS;

ACIDS; CARBONYLATION; CATALYSIS; CATALYSTS; ENANTIOSELECTIVITY; RHODIUM; UNSATURATED COMPOUNDS;

RHODIUM COMPOUNDS;

BORONIC ACID DERIVATIVE; CARBONYL DERIVATIVE; RHODIUM; KETONE;

ARTICLE; ASYMMETRIC CATALYSIS; CATALYST; CHEMICAL STRUCTURE; ENANTIOMER; ENANTIOSELECTIVITY; MICHAEL ADDITION; ROOM TEMPERATURE; STEREOCHEMISTRY; SUBSTITUTION REACTION; SYNTHESIS; CATALYSIS; CHEMISTRY;

BORONIC ACIDS; CATALYSIS; KETONES; RHODIUM;

EID: 60849111703     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo802136j     Document Type: Article

References (18)

1. (a) The first generation catalyst: Takaya, Y.; Ogasawara, M.; Hayashi, T.; Sakai, M.; Miyaura, N. J. Am. Chem. Soc. 1998, 120, 5579.
2. (b) The second generation catalyst: Hayashi, T.; Takahashi, M.; Takaya, Y.; Ogasawara, M. J. Am. Chem. Soc. 2002, 724, 5052.
3. Itooka, R.; Iguchi, Y.; Miyaura, N. J. Org. Chem. 2003, 68, 6000.
4. For reviews, see: (a) Hayashi, T.; Yamasaki, K. Chem. Rev. 2003, 103, 2829.
5. (b) Hayashi, T. Synlett 2001, 879.
6. (a) Boiteau, J.-G.; Minnaard, A. J.; Feringa, B. J. Org. Chem. 2003, 68, 9481.
7. (b) Otomaru, Y.; Okamoto, K.; Shintani, R.; Hayashi, T. J. Org. Chem. 2005, 70, 2503.
8. (c) Paquin, J.-F.; Stephenson, C. R. J.; Defieber, G.; Carreira, E. M. J. Am. Chem. Soc. 2005, 127, 10850.
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11. (a) A solvent switch from water to isopropyl alcohol was recently reported to reduce the boronic acid loss due to protodeborylation: Brock, S.; Hose, D. R. J.; Mosely, J. D.; Parker, A. J.; Patel, I.; Williams, A. J. Org. Process Res. Dev. 2008, 12, 496.
12. 2 and KOH has been reported (ref 1b). However, the precursor complex is not available commercially. Additionally, formation of a racemic product was reported when utilizing the catalyst prepared in this way (ref 2).
13. Literature data for rhodium-catalyzed asymmetric additions of arylboronic acids to compounds 11-14: 11a, ref 1a; 11c,11d, ref 1b; 12b: Pucheault, M.; Darses, S.; Genet, J.-P. Eur. J. Org. Chem. 2002, 21, 3552. 12a,14, ref 2.
14. Experiments in R-series gave products with slightly lower chiral purities probably due to the lower chiral purity of the ligand used (99.3 vs 99.9% ee for S-series): 6, 96.1% ee; 11c, 93.2% ee; 11d, 96.6% ee; 12a, 98.8% ee; 12b, 99.1% ee; 13, 91.2% ee.
15. α,β-Unsaturated aldehydes have been reported to give poor yields/chiral purities in rhodium-binap-catalyzed additions of arylboronic acids. See, for example, ref 4c.
16. The reaction is exothermic with adiabatic heat of 40 °C. External cooling was used to maintain 23-27 °C temperature.
17. Literature refs for the isolated compounds. 6: Li, Z.; Chen, W.; Hale, J. J.; Lynch, C. L.; Mills, S. G.; Hajdu, R.; Keohane, C. A.; Rosenbach, M. J.; Milligan, J. A.; Shei, G.-J.; Chrebet, G.; Parent, S. A.; Bergstrom, J.; Card, D.; Forrest, M.; Quackenbush, E. J.; Wickham, L. A.; Vargas, H.; Evans, R. M.; Rosen, H.; Mandala, S. J. Med. Chem. 2005, 48, 6169. 11a: Paquette, L. A.; Gilday, J. P.; Ra, C. S. J. Am. Chem. Soc. 1987, 109, 6858. 11c,11d: Takaya, Y.; Ogasawara, M.; Hayashi, T. Tetrahedron Lett. 1999, 40, 6957. 12a: Barnhart, R. W.; Wang, X.; Noheda, P.; Bergens, S. H.; Whelan, J.; Bosnich, B. J. Am. Chem. Soc. 1994, 116, 1821. 12b: Zhang, Y.; Schuster, G. B. J. Org. Chem. 1994, 59, 1855. 13: Marugesan, N.; Barrish, J. C.; Lloyd, J. Jpn. Kokai Tokkyo Koho; Patent JP 09124620 A 19970513, 1997. 14: Ref 1a.
18. No further enhancement in the chiral purity of products was observed during the isolation.