Asymmetric hydrocyanation of α,β-unsaturated ketones into β-cyano ketones with the [Ru(phgly)2(binap)]/C6H 5OLi catalyst system

Angewandte Chemie - International Edition

Volumn 50, Issue 24, 2011, Pages 5541-5544

  Kurono, Nobuhito ^a   Nii, Noriyuki ^a   Sakaguchi, Yusuke ^a   Uemura, Masato ^a   Ohkuma, Takeshi ^a  

^a HOKKAIDO UNIVERSITY   (Japan)

Author keywords

, unsaturated ketones; asymmetric catalysis; hydrocyanation; lithium; ruthenium

Indexed keywords

ASYMMETRIC CATALYSIS; CATALYST SYSTEM; COMBINED SYSTEM; CYANATION; ENANTIOSELECTIVE CONJUGATE ADDITION; HIGH YIELD; HYDROCYANATION; MOLAR RATIO; UNSATURATED KETONES;

CATALYSIS; CATALYSTS; LITHIUM; ORGANIC COMPOUNDS; RUTHENIUM;

KETONES;

EID: 79958021809     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201100939     Document Type: Article

References (22)

1. HCN is a toxic compound, but it is utilized in industrial processes for the production of useful chemical compounds, such as α-hydroxy acids, α-amino acids, and methacrylates; for example, see:, P. Poechlauer, W. Skranc, M. Wubbolts, in Asymmetric Catalysis on Industrial Scale: Challenge, Approaches and Solutions (Eds.:, H.U. Blaser, E. Schmidt,), Wiley-VCH, Weinheim, 2004, pp. 151-164.
2. Y. Tanaka, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2008, 130, 6072-6073
3. Y. Tanaka, M. Kanai, M. Shiabasaki, J. Am. Chem. Soc. 2010, 132, 8862-8863.
4. For cyanation of α,β-unsaturated imides, see G. M. Sammis, E. N. Jacobsen, J. Am. Chem. Soc. 2003, 125, 4442-4443
5. G. M. Sammis, H. Danjo, E. N. Jacobsen, J. Am. Chem. Soc. 2004, 126, 9928-9929
6. C. Mazet, E. N. Jacobsen, Angew. Chem. 2008, 120, 1786-1789
7. Angew. Chem. Int. Ed. 2008, 47, 1762-1765
8. N. Madhavan, M. Weck, Adv. Synth. Catal. 2008, 350, 419-425.
9. For cyanation of α,β-unsaturated N-acylpyrroles, see T. Mita, K. Sasaki, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2005, 127, 514-515
10. I. Fujimori, T. Mita, K. Maki, M. Shiro, A. Sato, S. Furusho, M. Kanai, M. Shibasaki, Tetrahedron 2007, 63, 5820-5831.
11. For cyanation of other activated alkenes using acetone cyanohydrin or ethyl cyanoformate as a cyanide source, see L. Bernardi, F. Fini, M. Fochi, A. Ricci, Synlett 2008, 1857-1861
12. J. Wang, W. Li, Y. Liu, Y. Chu, L. Lin, X. Liu, X. Feng, Org. Lett. 2010, 12, 1280-1283.
13. Use of pure HCN as a cyanide source gave low yield and enantioselectivity in the reaction with the Gd catalyst. The Sr catalyst is expected to be labile in the presence of a large excess of HCN; for details see reference[2].
14. N. Kurono, K. Arai, M. Uemura, T. Ohkuma, Angew. Chem. 2008, 120, 6745-6748
15. Angew. Chem. Int. Ed. 2008, 47, 6643-6646
16. N. Kurono, M. Uemura, T. Ohkuma, Eur. J. Org. Chem. 2010, 1455-1459.
17. N. Kurono, T. Yoshikawa, M. Yamasaki, T. Ohkuma, Org. Lett. 2011, 13, 1254-1257.
18. O. Glemser, in Handbook of Preparative Inorganic Chemistry, 2 nd ed., (Eds.: G. Brauer, R.F. Riley,), Academic Press, New York, 1963, pp. 658-660.
19. Tol-binap=2,2′-bis(di-4-tolylphosphanyl)-1,1′-binaphthyl.
20. The β-amino ketones 2 in 88%ee and 2s in 92%ee were obtained by Shibasaki's Gd system (see reference[2a]).
21. 3SiCN to 1h catalyzed by a chiral sodium phosphate with an S/C of 5 gave 2h in 71%ee. See:, J. Yang, S. Wu, F.-X. Chen, Synlett 2010, 2725-2728.
22. R. V. Hoffman, H.-O. Kim, J. Org. Chem. 1995, 60, 5107-5113.