Enantiomerically pure 2-piperazinemethanols as novel chiral ligands of oxazaborolidine catalysts in enantioselective borane reductions

Tetrahedron Letters

Volumn 40, Issue 29, 1999, Pages 5379-5382

  Inoue, Tsutomu ^a   Sato, Daisuke ^a   Komura, Kenichi ^b   Itsuno, Shinichi ^b  

^a NIPPON SODA CO LTD   (Japan)

^b TOYOHASHI UNIVERSITY OF TECHNOLOGY   (Japan)

Author keywords

Asymmetric reduction; Ketones; Oxime ethers; Piperazinemethanol

Indexed keywords

2 PIPERAZINEMETHANOL; PIPERAZINE DERIVATIVE; UNCLASSIFIED DRUG;

ANALYTIC METHOD; ARTICLE; CATALYSIS; CHEMICAL BOND; CHEMICAL REACTION; ENANTIOMER; SYNTHESIS;

EID: 0033575420     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01031-X     Document Type: Article

References (17)

1. S. Itsuno, Organic Reactions, John Wiley & Sons., 1998, 52, Chapter 2, 395. S. Itsuno, Comprehensive Asymmetric Catalysis, E. N. Jacobsen, A. Pfaltz and H. Yamamoto, eds., Chapter 6, Springer, in press. E. J.Corey and C. J. Helal, Angew. Chem. Int. Ed., 1998, 37, 1986.
2. S. Itsuno, Organic Reactions, John Wiley & Sons., 1998, 52, Chapter 2, 395. S. Itsuno, Comprehensive Asymmetric Catalysis, E. N. Jacobsen, A. Pfaltz and H. Yamamoto, eds., Chapter 6, Springer, in press. E. J.Corey and C. J. Helal, Angew. Chem. Int. Ed., 1998, 37, 1986.
3. S. Itsuno, Organic Reactions, John Wiley & Sons., 1998, 52, Chapter 2, 395. S. Itsuno, Comprehensive Asymmetric Catalysis, E. N. Jacobsen, A. Pfaltz and H. Yamamoto, eds., Chapter 6, Springer, in press. E. J. Corey and C. J. Helal, Angew. Chem. Int. Ed., 1998, 37, 1986.
4. Both enantiomers and racemate of 1 are available from Nippon Soda Co. Ltd. (Fax: +81-3-3245-6059)
5. A typical experimental procedure for the enantioselective reduction of acetophenone: To a solution of amino alcohol 3 (0.74 mmol) in THF (4 ml) was added a THF solution of borane dimethylsulfide (7.32 mmol) at 0 °C, and the mixture was refluxed for 1 h to complete the formation of the chiral oxazaborolidine. Then THF (1 ml) solution of acetophenone (3.66 mmol) was added dropwise to the above solution at 0 °C. The reaction mixture was stirred for 18 h at 0 °C and quenched with 3M HCl aqueous solution. After usual workup, the crude product was chromatographed on silica gel to afford 1-phenylethanol. Enantioselectivity was determined by HPLC analysis using CHIRALCEL OJ.
6. Stable conformations (A, B) of the oxazaborolidines derived from (R)-3a and (R)-3d were estimated by MOPAC-AM1 calculation. The toluene (A) and naphthalene (B) moieties seem to shield the opposite approach of the substrate effectively. (formula presented)
7. D. Enders and U. Reinhold, Tetrahedron: Asymmetry, 1997, 8, 1895. S. E. Denmark and O. J. -C.Nicaise, Chem. Commun., 1996, 999.
8. D. Enders and U. Reinhold, Tetrahedron: Asymmetry, 1997, 8, 1895. S. E. Denmark and O. J. -C. Nicaise, Chem. Commun., 1996, 999.
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10. S. R. Landor, Y. M. Chan, O. O. Sonola and A. R. Tatchell, J. Chem. Soc., Perkin Trans. I, 1984, 493. S. Itsuno, Y. Sakurai, K. Shimizu and K. Ito, J. Chem. Soc., Perkin 1, 1990, 1859. J. T. Dougherty, J. R.Flisak, J. Hayes, I. Lantos, L. Liu and L. Tucker, Tetrahedron: Asymmetry, 1997, 8, 497. C. Bolm and M.Felder, Synlett, 1994, 655. M. Masui and T. Shioiri, Tetrahedron Lett., 1998, 39, 5195.
11. S. R. Landor, Y. M. Chan, O. O. Sonola and A. R. Tatchell, J. Chem. Soc., Perkin Trans. I, 1984, 493. S.Itsuno, Y. Sakurai, K. Shimizu and K. Ito, J. Chem. Soc., Perkin 1, 1990, 1859. J. T. Dougherty, J. R. Flisak, J. Hayes, I. Lantos, L. Liu and L. Tucker, Tetrahedron: Asymmetry, 1997, 8, 497. C. Bolm and M.Felder, Synlett, 1994, 655. M. Masui and T. Shioiri, Tetrahedron Lett., 1998, 39, 5195.
12. S. R. Landor, Y. M. Chan, O. O. Sonola and A. R. Tatchell, J. Chem. Soc., Perkin Trans. I, 1984, 493. S.Itsuno, Y. Sakurai, K. Shimizu and K. Ito, J. Chem. Soc., Perkin 1, 1990, 1859. J. T. Dougherty, J. R.Flisak, J. Hayes, I. Lantos, L. Liu and L. Tucker, Tetrahedron: Asymmetry, 1997, 8, 497. C. Bolm and M. Felder, Synlett, 1994, 655. M. Masui and T. Shioiri, Tetrahedron Lett., 1998, 39, 5195.
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17. A typical experimental procedure for the enantioselective reduction of acetophenone O-methyloxime: To a solution of amino alcohol 3 (1.36 mmol) in THF (7 ml) was added a THF solution of borane dimethylsulfide (2.72 mmol) at 0 °C, and the mixture was refluxed for 10 min to complete the formation of the chiral oxazaborolidine. Then THF (1 ml) solution of acetophenone O-methyloxime (1.36 mmol) was added dropwise to the above solution. The reaction mixture was stirred for 6 h at 50 °C and quenched with 3M HCl aqueous solution. After usual workup, the crude product was chromatographed on silica gel to afford 1-phenylethylamine. Enantioselectivity was determined for its N-ethoxycarbonyl derivative by HPLC analysis using CHIRALCEL OJ.