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The formation of bicyclic cyclopropanols in very low yield by interaction at room temperature of (ethoxy)(γ,δ-alkenyl)carbene complexes of tungsten with N-methyldihydropyridine has been tentatively explained through an intramolecular cyclopropanation of the double bond by an in situ generated N-methylpyridinium oxycarbene complex: H. Rudler, A. Parlier, T. Durand-Réville, B. Martín-Vaca, M. Audouin, E. Garrier, V. Certal, J. Vaissermann, Tetrahedron 2000, 56, 5001.
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0006598561
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note
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Alternatively, these carbene complexes can be prepared from pentacarbonyl[1-[(tetramethylammonio)oxy]ethylidene]chromium by the acylation/haloalcohol exchange/benzaldehyde condensation sequence (see Experimental Section).
-
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30
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0001024887
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and ref. [9c]
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For compounds containing the tetrahydrofuran-2-spiro-1′-cyclopropane ring system, see: A. de Meijere, I. Erden, W. Weber, D. Kaufmann, J. Org. Chem. 1988, 53, 152 and ref. [9c].
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0006598562
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For compounds containing the tetrahydropyran-2-spiro-1′-cyclopropane ring system, see for example: A. Vasella, C. A. A. Waldraff, Helv. Chim. Acta 1991, 74, 585 and references therein.
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0006628403
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note
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The one-pot oxaspirocyclopropanation reaction was examined with carbene complex 1a and cyclohexene. After heating in THF at 120°C for 1 h, either two or four equivalents of Li-naphthalene were added at -78°C and the mixtures stirred for 15 min or 2 h, respectively. Final hydrolysis at -78°C for each experiment provided a mixture of 2-chloroethoxycyclopropane 4 a (major product) and oxaspyrocyclopropane 8a (always as a minor component).
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0006628641
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G. D. Sargent, J. N. Cron, S. Bank, J. Am. Chem. Soc. 1966, 88, 5363.
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0006598563
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In addition, the tendency of the 5-hexen-1-yl radical to cyclize to the cyclopentylmethyl radical is well documented: c) R. C. Lamb, P. W. Ayers, M. K. Toney, J. F. Garst, J. Am. Chem. Soc. 1966, 88, 4261 and references therein.
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0006612542
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The preference for exo-cyclization of 6-hepten-1-yl radicals is known: R. A. Batey, D. V. Smil, Angew. Chem. 1999, 111, 1914;
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We have observed that cyclopropanols 13-16 are unstable and upon standing even under nitrogen and when refrigerated (8-10°C), they slowly decompose to a mixture of carbonyl-containing products. Thermal isomerization of tertiary cyclopropanols to ketones has been described: a) J. T. Groves, K. W. Ma, Tetrahedron Lett. 1974, 909;
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