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Volumn 63, Issue 9, 1998, Pages 2854-2857

Steric Hindrance Facilitated Synthesis of Enynes and Their Intramolecular [4 + 2] Cycloaddition with Alkynes

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EID: 0041666031     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9717853     Document Type: Article
Times cited : (35)

References (60)
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  • 12
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    • For reactions of this type that proceed through cationic intermediates, see: (a) Whitlock, H.; Wu, W. E.-M.; Whitlock, B. J. J. Org. Chem. 1969, 34, 1857. (b) Hoffmann, H. M. R.; Krumwiede, D.; Mucha, B.; Oehlerking, H. H.; Prahst, G. W. Tetrahedron 1993, 49, 8999. (c) Miller, B.; Ionescu, D. Tetrahedron Lett. 1994, 35, 6615.
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    • note
    • 4 cat., 90°C, acetonitrile or pyrrolidine].
  • 19
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    • Self-coupling of 2 gave variable amounts of regioisomeric butenynes and the diyne as byproducts.
    • (a) Self-coupling of 2 gave variable amounts of regioisomeric butenynes and the diyne as byproducts.
  • 20
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    • 2 (80% D) in pyrrolidine-N-d (65% D).
    • 2 (80% D) in pyrrolidine-N-d (65% D).
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    • note
    • 15b However, this process could be considered as a type I Cyclization.
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    • note
    • 3N (1 equiv), toluene, 23°C, 12 h; 60%, 83% based on unrecovered 1].
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    • 1H NMR spectra with that of 4
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    • note
    • 11
  • 28
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    • The configuration of enyne 19, isolated as a single isomer, was not determined
    • (c) The configuration of enyne 19, isolated as a single isomer, was not determined.
  • 29
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    • 2O (5 mol %), pyrrolidine, 50°C, 16 h] although the isolated yield was low (8%). See Experimental Section for details.
  • 39
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    • The regiochemistry of the insertion is contrary to that observed in the Heck reaction between iodoarenes and disubstituted alkynes similar to those used in this work: Arcadi, A.; Cacchi, S.; Marinelli, F. Tetrahedron 1985, 41, 5121.
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    • 25b (60% yield)
    • 25b (60% yield),
  • 44
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    • note
    • 2/LiCl (pyridine solutions), which suggests that Cu(I) is the actual catalyst.
  • 45
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    • note
    • Protonation of the alkyne by the pyrrolidinium salts, which are soluble under the reaction conditions, may play a role in the process. Piperidinium iodide is insoluble in neat piperidine at room temperature.
  • 46
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    • note
    • The regiochemistry of 4 was determined on the basis of HMQC and HMBC experiments. Its configuration was determined on the basis of NOESY experiments (800 and 400 ms mixing time).
  • 59
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    • 2,6-Dimethyl-5-methylidene-3-heptyne-2,6-diol, obtained as a byproduct in some of the couplings of alkyne 2, was prepared according to the published procedure: Trost, B. M.; Sorum, M. T.; Chan, C.; Harms, A. E.; Rühter, G. J. Am. Chem. Soc. 1997, 119, 698.
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    • Trost, B.M.1    Sorum, M.T.2    Chan, C.3    Harms, A.E.4    Rühter, G.5


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