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Volumn 61, Issue 3, 1996, Pages 868-873

BCl3- and TiCl4-mediated reductions of β-hydroxy ketones

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Indexed keywords


EID: 0000723466     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo951549x     Document Type: Article
Times cited : (51)

References (58)
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    • For the most recent work in this area, see the following and references cited therein (a) Bonini, C.; Racioppi, R.; Righi, G.; Rossi, L. Tetrahedron. Asymmetry 1994, 5, 173-176. (b) Kaneko, Y.; Matsuo, T.; Kiyooka, S. Tetrahedron Lett. 1994, 35, 4107-4110. (c) Mohr, P. Tetrahedron Lett. 1991, 32, 2219-2222. (d) Bonini, C.; Bianco, A.; Di Fabio, R.; Mecozzi, S.; Proposito, A., Righi, G. Gazz. Chim. Ital. 1991, 121, 75-80. (e) Evans, D. A.; Hoveyda, A. H. J Org. Chem. 1990, 55, 5190-5192. (f) Evans, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1990, 112, 6447-6449.
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    • For the most recent work in this area, see the following and references cited therein (a) Bonini, C.; Racioppi, R.; Righi, G.; Rossi, L. Tetrahedron. Asymmetry 1994, 5, 173-176. (b) Kaneko, Y.; Matsuo, T.; Kiyooka, S. Tetrahedron Lett. 1994, 35, 4107-4110. (c) Mohr, P. Tetrahedron Lett. 1991, 32, 2219-2222. (d) Bonini, C.; Bianco, A.; Di Fabio, R.; Mecozzi, S.; Proposito, A., Righi, G. Gazz. Chim. Ital. 1991, 121, 75-80. (e) Evans, D. A.; Hoveyda, A. H. J Org. Chem. 1990, 55, 5190-5192. (f) Evans, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1990, 112, 6447-6449.
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    • For the most recent work in this area, see the following and references cited therein (a) Bonini, C.; Racioppi, R.; Righi, G.; Rossi, L. Tetrahedron. Asymmetry 1994, 5, 173-176. (b) Kaneko, Y.; Matsuo, T.; Kiyooka, S. Tetrahedron Lett. 1994, 35, 4107-4110. (c) Mohr, P. Tetrahedron Lett. 1991, 32, 2219-2222. (d) Bonini, C.; Bianco, A.; Di Fabio, R.; Mecozzi, S.; Proposito, A., Righi, G. Gazz. Chim. Ital. 1991, 121, 75-80. (e) Evans, D. A.; Hoveyda, A. H. J Org. Chem. 1990, 55, 5190-5192. (f) Evans, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1990, 112, 6447-6449.
    • (1991) Tetrahedron Lett. , vol.32 , pp. 2219-2222
    • Mohr, P.1
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    • 0013590923 scopus 로고
    • For the most recent work in this area, see the following and references cited therein (a) Bonini, C.; Racioppi, R.; Righi, G.; Rossi, L. Tetrahedron. Asymmetry 1994, 5, 173-176. (b) Kaneko, Y.; Matsuo, T.; Kiyooka, S. Tetrahedron Lett. 1994, 35, 4107-4110. (c) Mohr, P. Tetrahedron Lett. 1991, 32, 2219-2222. (d) Bonini, C.; Bianco, A.; Di Fabio, R.; Mecozzi, S.; Proposito, A., Righi, G. Gazz. Chim. Ital. 1991, 121, 75-80. (e) Evans, D. A.; Hoveyda, A. H. J Org. Chem. 1990, 55, 5190-5192. (f) Evans, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1990, 112, 6447-6449.
    • (1991) Gazz. Chim. Ital. , vol.121 , pp. 75-80
    • Bonini, C.1    Bianco, A.2    Di Fabio, R.3    Mecozzi, S.4    Proposito, A.5    Righi, G.6
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    • 0001048937 scopus 로고
    • For the most recent work in this area, see the following and references cited therein (a) Bonini, C.; Racioppi, R.; Righi, G.; Rossi, L. Tetrahedron. Asymmetry 1994, 5, 173-176. (b) Kaneko, Y.; Matsuo, T.; Kiyooka, S. Tetrahedron Lett. 1994, 35, 4107-4110. (c) Mohr, P. Tetrahedron Lett. 1991, 32, 2219-2222. (d) Bonini, C.; Bianco, A.; Di Fabio, R.; Mecozzi, S.; Proposito, A., Righi, G. Gazz. Chim. Ital. 1991, 121, 75-80. (e) Evans, D. A.; Hoveyda, A. H. J Org. Chem. 1990, 55, 5190-5192. (f) Evans, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1990, 112, 6447-6449.
    • (1990) J Org. Chem. , vol.55 , pp. 5190-5192
    • Evans, D.A.1    Hoveyda, A.H.2
  • 7
    • 0013590923 scopus 로고
    • For the most recent work in this area, see the following and references cited therein (a) Bonini, C.; Racioppi, R.; Righi, G.; Rossi, L. Tetrahedron. Asymmetry 1994, 5, 173-176. (b) Kaneko, Y.; Matsuo, T.; Kiyooka, S. Tetrahedron Lett. 1994, 35, 4107-4110. (c) Mohr, P. Tetrahedron Lett. 1991, 32, 2219-2222. (d) Bonini, C.; Bianco, A.; Di Fabio, R.; Mecozzi, S.; Proposito, A., Righi, G. Gazz. Chim. Ital. 1991, 121, 75-80. (e) Evans, D. A.; Hoveyda, A. H. J Org. Chem. 1990, 55, 5190-5192. (f) Evans, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1990, 112, 6447-6449.
    • (1990) J. Am. Chem. Soc. , vol.112 , pp. 6447-6449
    • Evans, D.A.1    Hoveyda, A.H.2
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    • 13C NMR spectroscopies, see: (a) House, H. O.; Crumrine, D. S.; Teranishi, A. Y.; Olmstead, H. D. J. Am. Chem. Soc. 1973, 95, 3310-3324. (b) Heathcock, C. H.; Pirrung, M. C.; Sohn, J. E. J. Org Chem. 1979, 44, 4294-4299.
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    • note
    • 2 were substituted successfully for reducing agents with the syn-to-anti ratio exceeding 98:2 and 74-87% yields.
  • 20
    • 85088622062 scopus 로고    scopus 로고
    • note
    • 3 led to 69:31 (84%) and 60:40 (81%) syn-to-anti ratios, respectively.
  • 23
  • 24
  • 30
    • 85088621119 scopus 로고    scopus 로고
    • note
    • 3, 87:13.
  • 31
    • 5344248133 scopus 로고    scopus 로고
    • note
    • Derived from molecular mechanics (PCMODEL Version 4.51: Serena Software, Bloomington, IN 47402), strain energies (kcal/mol for the following isomers of 1-chloro-3-methylcyclohexane: cis, all equatorial -7.19, all axial -10.63; trans, chloride axial -7.63, methyl axial -8.96.
  • 32
    • 5344228543 scopus 로고    scopus 로고
    • note
    • Another boat conformer with the stereogenic methyl occupying a pseudoaxial site could not be found.
  • 33
    • 85088619337 scopus 로고    scopus 로고
    • note
    • 11B NMR: see ref 19b.
  • 34
    • 85088620916 scopus 로고    scopus 로고
    • note
    • 3 (bp 12.5 °C).
  • 35
    • 0000144120 scopus 로고
    • See, for example: (a) Keck, G E.; Castellino, S. J. Am. Chem. Soc. 1986, 108, 3847-3849. (b) Keck, G. E.; Castellino, S.; Wiley, M. R. J. Org Chem. 1986, 51, 5480-5482. (c) Keck, G. E.; Castellino, S. Tetrahedron Lett. 1987, 28, 281-284.
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  • 36
    • 0000144120 scopus 로고
    • See, for example: (a) Keck, G E.; Castellino, S. J. Am. Chem. Soc. 1986, 108, 3847-3849. (b) Keck, G. E.; Castellino, S.; Wiley, M. R. J. Org Chem. 1986, 51, 5480-5482. (c) Keck, G. E.; Castellino, S. Tetrahedron Lett. 1987, 28, 281-284.
    • (1986) J. Org Chem. , vol.51 , pp. 5480-5482
    • Keck, G.E.1    Castellino, S.2    Wiley, M.R.3
  • 37
    • 0000824747 scopus 로고
    • See, for example: (a) Keck, G E.; Castellino, S. J. Am. Chem. Soc. 1986, 108, 3847-3849. (b) Keck, G. E.; Castellino, S.; Wiley, M. R. J. Org Chem. 1986, 51, 5480-5482. (c) Keck, G. E.; Castellino, S. Tetrahedron Lett. 1987, 28, 281-284.
    • (1987) Tetrahedron Lett. , vol.28 , pp. 281-284
    • Keck, G.E.1    Castellino, S.2
  • 38
    • 5344223574 scopus 로고    scopus 로고
    • note
    • See Experimental Section for more details.
  • 39
    • 85088621353 scopus 로고    scopus 로고
    • note
    • 3 at rt. Our experience is that chemical shifts of such compounds are not greatly dependent on temperature or the chlorinated solvent used.
  • 41
    • 0003942864 scopus 로고
    • Wiley: New York
    • This is a large part of the 4.6-6.2 kcal/mol destabilization of the twist form of cyclohexane relative to the chair form, see: Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; Wiley: New York, 1994; pp 689-690.
    • (1994) Stereochemistry of Organic Compounds , pp. 689-690
    • Eliel, E.L.1    Wilen, S.H.2
  • 42
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    • note
    • Six hours of stirring is sufficient at this point. If an ester is present in the substrate, transesterification has been observed with the longer reaction time.


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