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Volumn 73, Issue 2, 2008, Pages 741-744

An environmentally benign synthesis of cis-2,6-disubstituted tetrahydropyrans via indium-mediated tandem allylation/prins cyclization reaction

Author keywords

[No Author keywords available]

Indexed keywords

CYCLIZATION; INDIUM; SYNTHESIS (CHEMICAL);

EID: 40949116624     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo7016857     Document Type: Article
Times cited : (51)

References (45)
  • 1
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    • For a recent review of strategies for the formation of tetrahydropyran rings in the synthesis of natural products, see: (a) Clarke, P.A, Santos, S, Chem. 2006, 9, 2045
    • For a recent review of strategies for the formation of tetrahydropyran rings in the synthesis of natural products, see: (a) Clarke, P.A.; Santos, S. Eur. J. Org. Chem. 2006, 9, 2045.
  • 2
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    • For examples of 2,6-disubstituted tetrahydropyrans in natural product synthesis, see: (b) Clarke, P. A, Martin, W. H. C. Tetrahedron 2005, 61, 5433
    • For examples of 2,6-disubstituted tetrahydropyrans in natural product synthesis, see: (b) Clarke, P. A.; Martin, W. H. C. Tetrahedron 2005, 61, 5433.
  • 5
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    • For recent efforts toward the construction of tetrahydropyran rings, see: a
    • For recent efforts toward the construction of tetrahydropyran rings, see: (a) Clarke, P. A.; Martin, W. H. C. Tetrahedron Lett. 2004, 45, 9061.
    • (2004) Tetrahedron Lett , vol.45 , pp. 9061
    • Clarke, P.A.1    Martin, W.H.C.2
  • 12
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    • For indium-mediated tetrahydropyran and dihydropyran syntheses, see: a
    • For indium-mediated tetrahydropyran and dihydropyran syntheses, see: (a) Viswanathan, G. S.; Yang, J.; Li, C.-J. Org. Lett. 1999, 1, 993.
    • (1999) Org. Lett , vol.1 , pp. 993
    • Viswanathan, G.S.1    Yang, J.2    Li, C.-J.3
  • 19
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    • 3N, THF; NaI, acetone) from the corresponding allylic alcohol: Trost, B. M.; Chan, D. M. T.; Nanninga, N. Org. Synth. 1984, 62, 58.
    • 3N, THF; NaI, acetone) from the corresponding allylic alcohol: Trost, B. M.; Chan, D. M. T.; Nanninga, N. Org. Synth. 1984, 62, 58.
  • 21
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    • For the spectral data of 2a, see ref 3e
    • For the spectral data of 2a, see ref 3e.
  • 22
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    • Assessed by a simple litmus paper test
    • Assessed by a simple litmus paper test.
  • 23
    • 41149159679 scopus 로고    scopus 로고
    • As much as 50% of desilylated homoallylic alcohol was isolated from the reaction mixtures in some cases
    • As much as 50% of desilylated homoallylic alcohol was isolated from the reaction mixtures in some cases.
  • 24
    • 31944435336 scopus 로고    scopus 로고
    • For a discussion on erosion of enantioselectivity and side-chain exchange via the oxonium-Cope rearrangement in Prins reactions, see: (a) Cheng-Hsia, A. L, Loh, T.-P. Tetrahedron Lett. 2006, 47, 1641
    • For a discussion on erosion of enantioselectivity and side-chain exchange via the oxonium-Cope rearrangement in Prins reactions, see: (a) Cheng-Hsia, A. L.; Loh, T.-P. Tetrahedron Lett. 2006, 47, 1641.
  • 27
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    • Chan et al. have presented evidence that the intermediate in aqueous indium-mediated allylation reactions is allylindium(I): Chan, T. H.; Yang, T. J. Am. Chem. Soc. 1999, 121, 3228.
    • Chan et al. have presented evidence that the intermediate in aqueous indium-mediated allylation reactions is allylindium(I): Chan, T. H.; Yang, T. J. Am. Chem. Soc. 1999, 121, 3228.
  • 28
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    • 2, 0°C) followed by iodide displacement (NaI, acetone, rt, 24 h).
    • 2, 0°C) followed by iodide displacement (NaI, acetone, rt, 24 h).
  • 29
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    • 13C NMR) for 9 matched those reported by Hinkle for the same compound with syn-2,6- stereochemistry: (a) Lian, Y.; Hinkle, R. J. J. Org. Chem. 2006, 71, 7071.
    • 13C NMR) for 9 matched those reported by Hinkle for the same compound with syn-2,6- stereochemistry: (a) Lian, Y.; Hinkle, R. J. J. Org. Chem. 2006, 71, 7071.
  • 30
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    • Although Li reports the use of E-vinylsilanes for the synthesis of dihydropyrans (ref 3a, Brimble reports that the Z-configuration of the vinylsilane is crucial for the formation of dihydropyrans: (b) Meilert, K, Brimble, M. A. Org. Biolom. Chem. 2006, 4, 2184
    • Although Li reports the use of E-vinylsilanes for the synthesis of dihydropyrans (ref 3a), Brimble reports that the Z-configuration of the vinylsilane is crucial for the formation of dihydropyrans: (b) Meilert, K.; Brimble, M. A. Org. Biolom. Chem. 2006, 4, 2184.
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    • For the preparation of 10, see: (a) Majetich, G.; Song, J.-S.; Ringold, C.; Nemeth, G. A.; Newton, M. G. J. Org. Chem. 1991, 56, 3973.
    • For the preparation of 10, see: (a) Majetich, G.; Song, J.-S.; Ringold, C.; Nemeth, G. A.; Newton, M. G. J. Org. Chem. 1991, 56, 3973.
  • 33
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    • For an alternative preparation of cyclohexenyl-fused pyrans, see
    • For an alternative preparation of cyclohexenyl-fused pyrans, see: Loh, T.-P.; Feng, L.-C.; Yang, J.-Y. Synthesis 2002, 7, 937.
    • (2002) Synthesis , vol.7 , pp. 937
    • Loh, T.-P.1    Feng, L.-C.2    Yang, J.-Y.3
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    • 3N, THF), and iodide displacement (NaI, acetone, rt, 24 h).
    • 3N, THF), and iodide displacement (NaI, acetone, rt, 24 h).
  • 35
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    • 2).
    • 2).
  • 44
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    • 13C) for 13 were in complete accord with those reported for this compound by Clarke et al. (ref 20).
    • 13C) for 13 were in complete accord with those reported for this compound by Clarke et al. (ref 20).


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