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The carbamates 8 and 9 and related compounds all adopt a conformation in which the methyl group is axial to avoid allylic strain.
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For cyclization of allenes bearing a proximate nitrogen nucleophile, see: (a) Prasad, J. S.; Liebeskind, L. S. Tetrahedron Lett. 1988, 29, 4253. (b) Arseniyadis, S.; Gore, J. Tetrahedron Lett. 1983, 24, 3997. (c) Arseniyadis, S.; Sartoretti, J. Tetrahedron Lett. 1985, 26, 729. (d) Lathbury, D.; Gallagher, T. J. Chem. Soc., Chem. Commun. 1986, 114. (e) Kinsman, R.; Lathbury, D.; Vernon, P.; Gallagher, T. J. Chem. Soc., Chem. Commun. 1987, 243. (f) Shaw, R. W.; Gallagher, T. J. Chem. Soc., Perkin Trans. 1 1994, 3549.
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and references therein
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3 (0.3 equiv) in aqueous acetone, a δ-amino allenyl alkyne underwent cyclization without complication.
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Yields given in Scheme 14 are based on recovered starting triflate (13-18%)
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Yields given in Scheme 14 are based on recovered starting triflate (13-18%).
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78
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0344987592
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Reference 7b
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(a) Reference 7b.
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(b) Use of the allylic o-nitrobenzeneselenoxide resulted in the [2,3]-sigmatropic rearrangement to provide the 1,3-transposed allylic alcohol. Lability of allylic selenoxides, even in the absence of trapping agents other than adventitious moisture, was previously noted by Reich.
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