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Synlett 2004(8): 1383-1386  
DOI: 10.1055/s-2004-829093
LETTER
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Hydrogenation of 2-Arylated Cycloalkanones through Dynamic Kinetic Resolution

Takeshi Ohkuma, Jing Li, Ryoji Noyori*
Department of Chemistry and Research Center for Materials Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan
Fax: +81(52)7834177; e-Mail: noyori@chem3.chem.nagoya-u.ac.jp;
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Publikationsverlauf

Received 1 March 2004
Publikationsdatum:
22. Juni 2004 (online)

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Abstract

Asymmetric hydrogenation of 2-arylcycloalkanones with trans-RuCl2(binap)(1,2-diamine) and t-C4H9OK in 2-propanol selectively gives the corresponding cis-2-arylcycloalkanols in excellent enantiomeric purity and high yield. Two synthetic intermediates of biologically active compounds have been prepared by this method.

Key words

2-arylcycloalkanones - asymmetric hydrogenation - ­BINAP - dynamic kinetic resolution - ruthenium complexes

    References

  • 1 Noyori R. Tokunaga M. Kitamura M. Bull. Chem. Soc. Jpn.  1995,  68:  36 
    CrossrefPubMedGoogle Scholar
  • 2 For the first example, see: Noyori R. Ikeda T. Ohkuma T. Widhalm M. Kitamura M. Takaya H. Akutagawa S. Sayo N. Saito T. Taketomi T. Kumobayashi H. J. Am. Chem. Soc.  1989,  111:  9134 
    CrossrefGoogle Scholar
  • 3a Noyori R. Ohkuma T. Angew. Chem. Int. Ed.  2001,  40:  40 
    CrossrefPubMedGoogle Scholar
  • 3b

    BINAP = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl. TolBINAP = 2,2′-bis(di-4-tolylphosphino)-1,1′-binaphthyl. XylBINAP = 2,2′-bis(di-3,5-xylylphosphino)-1,1′-binaphthyl. DAIPEN = 1,1-di(4-anisyl)-2-isopropyl-1,2-ethylenediamine. DPEN = 1,2-diphenylethylene diamine.
    CrossrefPubMed
  • 4a Ohkuma T. Ooka H. Hashiguchi S. Ikariya T. Noyori R. J. Am. Chem. Soc.  1995,  117:  2675 
    CrossrefGoogle Scholar
  • 4b Ohkuma T. Ooka H. Ikariya T. Noyori R. J. Am. Chem. Soc.  1995,  117:  10417 
    CrossrefGoogle Scholar
  • 4c Ohkuma T. Ikehira H. Ikariya T. Noyori R. Synlett  1997,  467 
    CrossrefGoogle Scholar
  • 4d Doucet H. Ohkuma T. Murata K. Yokozawa T. Kozawa M. Katayama E. England AF. Ikariya T. Noyori R. Angew. Chem. Int. Ed.  1998,  37:  1703 
    CrossrefGoogle Scholar
  • 4e 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 
    CrossrefGoogle Scholar
  • 4f Ohkuma T. Koizumi M. Ikehira H. Yokozawa T. Noyori R. Org. Lett.  2000,  2:  659 
    CrossrefGoogle Scholar
  • 4g Ohkuma T. Koizumi M. Yoshida M. Noyori R. Org. Lett.  2000,  2:  1749 
    CrossrefGoogle Scholar
  • 4h Ohkuma T. Takeno H. Honda Y. Noyori R. Adv. Synth. Catal.  2001,  343:  369 
    CrossrefGoogle Scholar
  • 5 Ohkuma T. Ooka H. Yamakawa M. Ikariya T. Noyori R. J. Org. Chem.  1996,  61:  4872 
    Google Scholar
  • 6 Matsumoto T. Murayama T. Mitsuhashi S. Miura T. Tetrahedron Lett.  1999,  40:  5043 
    CrossrefGoogle Scholar
  • 7 Ohkuma T. Ishii D. Takeno H. Noyori R. J. Am. Chem. Soc.  2000,  122:  6510 
    CrossrefGoogle Scholar
  • 8 For the kinetic resolution of racemic ketones with RuH(η1-BH4)(binap)(dpen) under base-free conditions, see: Ohkuma T. Koizumi M. Muñiz K. Hilt G. Kabuto C. Noyori R. J. Am. Chem. Soc.  2002,  124:  6508 
    CrossrefPubMedGoogle Scholar
  • 9 For the mechanism of asymmetric hydrogenation of simple ketones with the BINAP-DPEN-Ru(II) catalyst, see: Sandoval CA. Ohkuma T. Muñiz K. Noyori R. J. Am. Chem. Soc.  2003,  125:  13490 
    CrossrefGoogle Scholar
  • See for example:
  • 10a Brown HC. Krishnamurthy S. Tetrahedron  1979,  35:  567 
    CrossrefGoogle Scholar
  • 10b Greeves N. In Comprehensive Organic Synthesis   Vol. 8:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  p.1 
    CrossrefGoogle Scholar
  • 10c Davis AP. In Houben-Weyl   4th ed., Vol. E21d:  Helmchen G. Hoffmann RW. Mulzer J. Schaumann E. Thieme; Stuttgart: 1995.  p.4025 
    CrossrefGoogle Scholar
  • 12

    Experimental Procedure of the Hydrogenation of 2a with Ketone:Ru = 100,000:1. Solid (R,RR)-7a (0.5 mg, 0.47 µmol), t-C4H9OK (180 mg, 1.73 mmol), and 2a (9.12 g, 51.2 mmol) were placed in a 500 mL glass autoclave equipped with a Teflon-coated magnetic stirring bar. Air present in the autoclave was replaced by argon. 2-Propanol (100 mL), which had been degassed by three freeze-thaw cycles, was added to the autoclave. The vessel was pressurized to 8 atm of hydrogen. The reaction mixture was vigorously stirred at 25 °C for 48 h, during which time the hydrogen cylinder was kept connected. After carefully venting the hydrogen gas in the apparatus, the solvent was removed under reduced pressure. The yield determined by GC was 100%. Subsequently, the residue was passed through a silica gel pad, eluted with a 1:4 EtOAc-hexane mixture giving (1S,2S)-5a (8.61 g, 93% yield, cis:trans = 100:0, 99.6% ee), [α]D 23 +103.6 (c 2.02, CH3OH) {lit. [α]D 27 -106 (c 0.20, CH3OH)},
    Crossref
  • 11b 1R,2R-Isomer: Verbit L. Price HC. J. Am. Chem. Soc.  1972,  94:  5143 
    CrossrefGoogle Scholar
  • 13a The absolute configuration of (1S,2S)-5b,c,e, and -6a, as well as (3S,4R)-12 was estimated according to the literature: Matsugi M. Itoh K. Nojima M. Hagimoto Y. Kita Y. Tetrahedron Lett.  2001,  42:  6903 
    CrossrefGoogle Scholar
  • 13b

    The cis alcohols were converted to the trans-(1R,2S) alcohols by stereoinversion of the hydroxyl-containing carbon, followed by acylation with 3β-acetoxy-Δ5-etiocholenic acid chloride. The 1H NMR chemical shift at C(18)-CH3 of the chiral auxiliary was higher than that derived from the 1S,2R-enantiomer.
    Crossref
  • 14 Lee J, Askin D, and Hoang T. inventors; US Pat. Appl.  20020019532. 
  • 16a Harrison T. Williams BJ. Swain CJ. Ball RG. Bioorg. Med. Chem. Lett.  1994,  4:  2545 
    CrossrefGoogle Scholar
  • 16b Stadler H. Bös M. Heterocycles  1999,  51:  1067 
    CrossrefGoogle Scholar
  • 17 Ladduwahetty T. Baker R. Cascieri MA. Chambers MS. Haworth K. Keown LE. MacIntyre DE. Metzger JM. Owen S. Rycroft W. Sadowski S. Seward EM. Shepheard SL. Swain CJ. Tattersall FD. Watt AP. Williamson DW. Hargreaves RJ. J. Med. Chem.  1996,  39:  2907 
    CrossrefGoogle Scholar
  • 18 Klioze SS, and Ehrgott FJ. inventors; US Pat.  4,312,876. 
  • 19a Hjorth S. Carlsson A. Clark D. Svensson K. Wikström H. Sanchez D. Lindberg P. Hacksell U. Arvidsson L.-E. Johansson A. Nilsson JLG. Psychopharmacol.  1983,  81:  89 
    CrossrefGoogle Scholar
  • 19b Herdeis C. Kaschinski C. Karla R. Lotter H. Tetrahedron: Asymmetry  1996,  7:  867 
    CrossrefGoogle Scholar
  • 19c Amat M. Cantó M. Llor N. Escolano C. Molins E. Espinosa E. Bosch J. J. Org. Chem.  2002,  67:  5343 
    CrossrefGoogle Scholar
15

Absolute configuration of (2S,3S)-10 was determined after removal of the N-benzyl group by hydrogenolysis. [15]