Asymmetric hydrogenation of tert-alkyl ketones

Journal of the American Chemical Society

Volumn 127, Issue 23, 2005, Pages 8288-8289

  Ohkuma, Takeshi ^b   Sandoval, Christian A ^a,c   Srinivasan, Rajagopal ^c   Lin, Quinghong ^a   Wei, Yinmao ^a   Muñiz, Kilian ^a   Noyori, Ryoji ^a  

^a NAGOYA UNIVERSITY   (Japan)

^b HOKKAIDO UNIVERSITY   (Japan)

^c NAGOYA INDUSTRIAL SCIENCE RESEARCH INSTITUTE   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL; HYDROGEN; KETONE DERIVATIVE; METHANOL; OLIGOMER; PICOLINIC ACID; RUTHENIUM DERIVATIVE; TERT ALKYL KETONE; UNCLASSIFIED DRUG;

ARTICLE; ATMOSPHERIC PRESSURE; CATALYST; CHIRALITY; DIASTEREOISOMER; ENANTIOSELECTIVITY; HYDROGENATION; PHOSPHORUS NUCLEAR MAGNETIC RESONANCE; PROTON NUCLEAR MAGNETIC RESONANCE;

EID: 20444437938     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja052071+     Document Type: Article

References (20)

1. For earlier efforts, see: (hydrogenation) (a) Nagel, U.; Roller, C. Z. Naturforsch. 1998, 53B, 267-270.
2. (b) Jiang, Q.; Jiang, Y.; Xiao, D.; Cao, P.; Zhang, X. Angew. Chem., Int. Ed. 1998, 37, 1100-1103.
3. (c) Ito, M.; Hirakawa, M.; Murata, K.; Ikariya, T. Organometallics 2001, 20, 379-381.
4. (Transfer hydrogenation with 2-propanol). (d) Nishibayashi, Y.; Takei, I.; Uemura, S.; Hidai, M. Organometallics 1999, 18, 2291-2293.
5. BINAP = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl. TolBINAP = 2,2′-bis(di-4-tolylphosphino)-1,1′-binaphthyl. DPEN = 1,2-diphenylethylene-diamine. Bipy = 2,2′-bipyridine.
6. (a) Noyori, R. Angew. Chem., Int. Ed. 2002, 41, 2005-2022.
7. (b) Noyori, R.; Ohkuma, T. Angew. Chem., Int. Ed. 2001, 40, 40-73.
8. (a) Doucet, H.; Ohkuma, T.; Murata, K.; Yokozawa, T.; Kozawa, M.; Katayama, E.; England, A. F.; Ikariya, T.; Noyori, R. Angew. Chem., Int. Ed. 1998, 37, 1703-1707.
9. (b) Ohkuma, T.; Koizumi, M.; Doucet, H.; Pham, T.; Kozawa, M.; Murata, K.; Katayama, E.; Yokozawa, T.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1998, 120, 13529-13530.
10. Ohkuma, T., Koizumi, M.; Muñiz, K.; Hilt, G.; Kabuto, C.; Noyori, R. J. Am. Chem. Soc. 2002, 124, 6508-6509.
11. Sandoval, C. A.; Ohkuma, T.; Muñiz, K.; Noyori, R. J. Am. Chem. Soc. 2003, 125, 13490-13503.
12. Hydrogenation of 1-tetralones is better effected by use of 1,4-diamine ligands in place of 1.2-diamines. See: Ohkuma, T.; Hattori, T.; Ooka, H.; Inoue, T.; Noyori, R. Org. Lett. 2004, 6, 2681-2683.
13. Kitamura, M.; Tokunasa, M.; Ohkuma, T.; Noyori, R. Org. Synth. 1993, 71, 1-13.
14. On occasion, minor uncharacterized species could be detected (<5%).
15. Ohkuma, T.; Ooka, H.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 10417-10418.
16. Tombo, G. M. R.; Bellus, D. Angew. Chem., Int. Ed. Engl. 1991, 30, 1193-1215.
17. Noyori, R.; Kitamura, M.; Ohkuma, T. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5356-5362.
18. 2[(S)-binap] under hard conditions (S/C = 200. 100 atm, 50 °C, 68 h) gave the S hydroxy ester in 96% ee and 100% yield. See: Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley: New York, 1994; Chapter 2.
19. Due to the group priority in nomenclature, (S)-2a,b,g,h and (R)-2d-f have the same β configuration.
20. 2[(S)-tolbinap][(S,S)-dpen] was considerably enhanced by use of ethanol in place of 2-propanol [(S)-2a in 14-82% ee and (R)-2d in 61-97% ee, respectively], albeit with moderate rate enhancement.