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Volumn 4, Issue 14, 2002, Pages 2445-2448

Oxiranyl anion-mediated synthesis of highly enantiomerically enriched styrene oxide derivatives

Author keywords

[No Author keywords available]

Indexed keywords

ALUMINUM DERIVATIVE; ALUMINUM LITHIUM HYDRIDE; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; EPOXIDE; ETHYLENE OXIDE; LIGAND; LITHIUM DERIVATIVE; REDUCING AGENT; STYRENE OXIDE;

EID: 0037062911     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol026212d     Document Type: Article
Times cited : (65)

References (48)
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    • 3). A solvent-dependent optical rotation sign has been also recently ascertained in the case of α-methylstyrene oxide (see: Archelas, A.; Furstoss, R. J. Org. Chem. 1999, 64, 6112-6114) and of other styrene oxide derivatives (see: Imanishi, H.; Katsuki, T. Tetrahedron Lett. 1997, 38, 251-254).
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    • 3). A solvent-dependent optical rotation sign has been also recently ascertained in the case of α-methylstyrene oxide (see: Archelas, A.; Furstoss, R. J. Org. Chem. 1999, 64, 6112-6114) and of other styrene oxide derivatives (see: Imanishi, H.; Katsuki, T. Tetrahedron Lett. 1997, 38, 251-254).
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    • note
    • Quantity of TMEDA less than 1 equiv led to the recovery of starting material and to minor yields of products.
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    • note
    • A computational and NMR investigation on the lithiated styrene oxide is underway and will be reported in due course.
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    • note
    • The convention employed for describing syn and anti diastereomers is as follows: if the main chain is written in an extended (zigzag) conformation, the diastereomer that has the oxiranyl ring and the hydroxy group both projecting either forward (bold bonds) or away from the viewer (dashed bonds) is called syn.
  • 35
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    • The anti stereoselection observed conforms to the empirical steric model for the prediction of the stereochemical outcome of reactions of chiral anions with aldehydes in the absence of chelation control, proposed by Bassindale and Taylor (Bassindale, A. R.; Ellis, R. J.; Lau, J. C.-Y.; Taylor, P. G. J. Chem. Soc., Chem. Commun. 1986, 98-100) and that has been also applied by Molander to explain the relative stereochemistry of the major diastereoisomer formed by oxiranyl anions addition to carbonyl compounds (Molander, G. A.; Mautner, K. J. Org. Chem. 1989, 54, 4042-4050). Probably, small energy differences between the two diastereomeric transition states could explain, also in our case, the low diastereoselectivity observed in the case of epoxy alcohols 3h-k.
    • (1986) J. Chem. Soc., Chem. Commun. , pp. 98-100
    • Bassindale, A.R.1    Ellis, R.J.2    Lau, J.C.-Y.3    Taylor, P.G.4
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    • The anti stereoselection observed conforms to the empirical steric model for the prediction of the stereochemical outcome of reactions of chiral anions with aldehydes in the absence of chelation control, proposed by Bassindale and Taylor (Bassindale, A. R.; Ellis, R. J.; Lau, J. C.-Y.; Taylor, P. G. J. Chem. Soc., Chem. Commun. 1986, 98-100) and that has been also applied by Molander to explain the relative stereochemistry of the major diastereoisomer formed by oxiranyl anions addition to carbonyl compounds (Molander, G. A.; Mautner, K. J. Org. Chem. 1989, 54, 4042-4050). Probably, small energy differences between the two diastereomeric transition states could explain, also in our case, the low diastereoselectivity observed in the case of epoxy alcohols 3h-k.
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    • Molander, G.A.1    Mautner, K.2
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    • note
    • Crystallographic data for compound (1R,2R)-3i have been deposited at the Cambridge Crystallographic Data Centre (deposition no. CCDC-186824). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, U.K. [fax: (int.) +44-1223/336-033; E-mail: deposit@ccdc.cam.ac.uk]. ORTEP view and CIF file for compound (1R, 2R)-3i have been also reported as Supporting Information.
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    • Rosini, C.; Scamuzzi, S.; Focati, M. P.; Salvadori, P. J. Org. Chem. 1995, 60, 8289-8293. Spectroscopic data of racemic (1R*,2S*)-1,2-diphenylpropane-1,2-diol were reported (Bach, T.; Kather, K. J. Org. Chem. 1996, 61, 3900-3901) and were also compared with those obtained by the ring opening of a sample of racemic (1R*,2R*)-3i, which gave the (1R*,2S*)-diol.
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    • Rosini, C.; Scamuzzi, S.; Focati, M. P.; Salvadori, P. J. Org. Chem. 1995, 60, 8289-8293. Spectroscopic data of racemic (1R*,2S*)-1,2-diphenylpropane-1,2-diol were reported (Bach, T.; Kather, K. J. Org. Chem. 1996, 61, 3900-3901) and were also compared with those obtained by the ring opening of a sample of racemic (1R*,2R*)-3i, which gave the (1R*,2S*)-diol.
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    • Bach, T.1    Kather, K.2
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    • note
    • The configuration at the tertiary benzylic carbon becomes S as the priority of the groups around this stereogenic centre is inverted in the opened product.
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    • note
    • 3, ee > 99%) of the enantiomer (R)-10.
  • 46
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    • note
    • Syn and anti diastereomeric epoxy alcohols 11 could be separated by preparative HPLC and spectroscopically characterized. Both resulted to be optically pure (er 99/1, by chiral HPLC) so testifying once more the configurational stability (S) of the corresponding α-lithiated p-chloro-substituted oxiranyllithium. The configuration to the carbinol carbon was assigned by analogy to the other epoxy alcohols.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.