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Volumn 125, Issue 47, 2003, Pages 14435-14445

Multicomponent Linchpin Couplings. Reaction of Dithiane Anions with Terminal Epoxides, Epichlorohydrin, and Vinyl Epoxides: Efficient, Rapid, and Stereocontrolled Assembly of Advanced Fragments for Complex Molecule Synthesis

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Indexed keywords

CHEMOSELECTIVITY ANALYSIS;

EID: 0344443340     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0376238     Document Type: Article
Times cited : (115)

References (90)
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    • Matsuda and co-workers previously reported an analogous unsymmetrical bisalkylation of trimethylsilylacetonitrile (19) with two different epoxides in DME (see scheme below). In this example, how the timing of the Brook rearrangement was controlled is unclear. One could speculate that the first alkylation occurs more rapidly that silyl migration. Alternatively, lithiated 19 could be more reactive that the intermediate formed after Brook rearrangement (21) reducing competitive alkylation. See: Matsuda, I.; Murata, S.; Ishii, Y. J. Chem. Soc., Perkin Trans. 1 1979, 26. (Diagram presented)
    • (1979) J. Chem. Soc., Perkin Trans. 1 , pp. 26
    • Matsuda, I.1    Murata, S.2    Ishii, Y.3
  • 29
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    • DMPU is an abbreviation for N,N′-dimethyl- N,N′-propylene urea. For substituting DMPU in place of HMPA, see: Mukhopadhyay, H.; Seebach, D. Helv. Chim. Acta 1982, 65, 385.
    • (1982) Helv. Chim. Acta , vol.65 , pp. 385
    • Mukhopadhyay, H.1    Seebach, D.2
  • 49
    • 0344887064 scopus 로고
    • a's of both the dithiane and benzylic protons are quite similar. See: Bordwell, F. G. Acc. Chem. Res. 1988, 21, 456.
    • (1988) Acc. Chem. Res. , vol.21 , pp. 456
    • Bordwell, F.G.1
  • 55
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    • The following scheme illustrates that the conformationally constrained 2-silyl-1,3-dithianes 56 and 58 furnish 57 and 59 upon treatment with benzaldehyde and a fluoride source. See: Capperucci, A.; Cere, V.; Degl'Innocenti, A.; Nocentini, T.; Pollicino, S. Synlett 2002, 9, 1447. (Diagram presented)
    • (2002) Synlett , vol.9 , pp. 1447
    • Capperucci, A.1    Cere, V.2    Degl'Innocenti, A.3    Nocentini, T.4    Pollicino, S.5
  • 64
    • 0012543140 scopus 로고    scopus 로고
    • For transition metal catalyzed reactions with vinyl epoxides, see: (d) Fagnou, K.; Lautens, M. Org. Lett. 2000, 2, 2319.
    • (2000) Org. Lett. , vol.2 , pp. 2319
    • Fagnou, K.1    Lautens, M.2
  • 66
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    • N2′ additions of organocuprates to vinyl epoxides, see: Marshall, J. A. Chem. Rev. 1989, 89, 1503.
    • (1989) Chem. Rev. , vol.89 , pp. 1503
    • Marshall, J.A.1
  • 77
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    • note
    • The relative configurations of the SN2 adducts derived from the cis and trans vinyl epoxides were determined by chemical correlation (see Supporting Information).
  • 81
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    • PhD. Thesis, Swiss Federal Institute of Technology, Zurich
    • (b) Denmark, S. E. PhD. Thesis, Swiss Federal Institute of Technology, Zurich, 1982.
    • (1982)
    • Denmark, S.E.1
  • 84
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    • note
    • Vinyl epoxide (±)-107 was prepared from commercially available trans, trans-2,4-hexadien-1-ol as shown in the following scheme: (Diagram presented) Vinyl epoxide (±)-110 was prepared from propargyl alcohol and Z-1-bromopropene as shown in the following scheme: (Diagram presented)
  • 85
    • 0344320214 scopus 로고    scopus 로고
    • See Supporting Information
    • See Supporting Information
  • 89
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    • note
    • 2O (ca. 0.2 M) at -78 °C, a cloudy suspension formed and gradually dissipated upon warming.
  • 90
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    • Vinyl epoxides (+)-117 and (+)-118 were prepared from the preceding alcohol as shown in the following scheme: (Diagram presented) For preparation of epoxy alcohol, see: Romero, A.; Wong, C. H. J. Org. Chem. 2000, 65, 8264.
    • (2000) J. Org. Chem. , vol.65 , pp. 8264
    • Romero, A.1    Wong, C.H.2


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