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Volumn 69, Issue 16, 2004, Pages 5275-5280

Cp2TiCl-promoted isomerization of trisubstituted epoxides to exo-methylene allylic alcohols on carvone derivatives

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOLS; CONTAMINATION; DERIVATIVES; SOLUTIONS; STEREOCHEMISTRY; SUBSTITUTION REACTIONS; THERMAL EFFECTS;

EID: 3543041830     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo049358u     Document Type: Article
Times cited : (36)

References (34)
  • 6
    • 0005208178 scopus 로고    scopus 로고
    • Renaud, P., Sibi, M. P., Eds; Wiley-VCH: Weinheim; Chapter 33
    • (c) Gansäuer, A.; Pierobon, M. In Radicals in Organic Synthesis; Renaud, P., Sibi, M. P., Eds; Wiley-VCH: Weinheim, 2001; Vol. 2, Chapter 3.3, pp 207-220.
    • (2001) Radicals in Organic Synthesis , vol.2 , pp. 207-220
    • Gansäuer, A.1    Pierobon, M.2
  • 12
    • 0035822901 scopus 로고    scopus 로고
    • A highly selective and efficient isomerization of the epoxide moiety of a dieneoxide (E)-ester to the corresponding exo-methylene allylic dieneol using palladium catalysis has been recently described with occasion of the synthesis of vitamin D fluoro analogues: (a) Kabat, M. M.; Garofalo, L. M.; Daniewski, A. R.; Hutchings, S. D.; Liu, W.; Okabe, M.; Radinov, R.; Zhou, T. J. Org. Chem. 2001, 66, 6141-6150.
    • (2001) J. Org. Chem. , vol.66 , pp. 6141-6150
    • Kabat, M.M.1    Garofalo, L.M.2    Daniewski, A.R.3    Hutchings, S.D.4    Liu, W.5    Okabe, M.6    Radinov, R.7    Zhou, T.8
  • 21
    • 3543035551 scopus 로고    scopus 로고
    • Experimental procedures for the preparation of 2a-5a, 11a, and 12a are provided in the Supporting Information. Similar transformations have been reported in the enantiomeric series starting from (R)-(-)-carvone: (a) Bermejo, F.; Rico-Ferreira, R.; Bamidele-Sanni, S.; García-Granda, S. J. Org. Chem. 2001, 66, 8257-8260.
    • (2001) J. Org. Chem. , vol.66 , pp. 8257-8260
    • Bermejo, F.1    Rico-Ferreira, R.2    Bamidele-Sanni, S.3    García-Granda, S.4
  • 23
    • 3543042221 scopus 로고    scopus 로고
    • note
    • 2 and fractionation of the reaction mixture by flash chromatography.
  • 28
    • 3542995422 scopus 로고    scopus 로고
    • note
    • If the titanium chloride attacks the radical (2) from the trans side, the resulting product has the Ti ring group and the acetate in a trans diequatorial conformation (3) that cannot lead to elimination. In order for the latter to occur, the ring would have to flip to a conformation with three axial groups, two of which are strongly eclipsed (4). It is likely that elimination in the direction of the methyl will occur instead in clear contradiction with our results. We are greatly indebted to the reviewer who suggested the cis elimination pathway to us prior to publication of this paper.
  • 29
    • 0000135630 scopus 로고
    • Paquette, L. A., Ed.; John Wiley & Sons, Inc.: New York
    • Nakai, T.; Mikami, K. In Organic Reactions; Paquette, L. A., Ed.; John Wiley & Sons, Inc.: New York, 1994; Vol. 46, p 105.
    • (1994) Organic Reactions , vol.46 , pp. 105
    • Nakai, T.1    Mikami, K.2
  • 30
    • 3543012926 scopus 로고    scopus 로고
    • note
    • See the Supporting Information for experimental details on the preparation of epoxides 1a-12a (Table 1).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.