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In contrast to a misleading statement in the literature (Besong, D. Billen, I. Dager, P. Kocienski, E. Sliwinski, L. R. Tai, and F. T. Boyle, Tetrahedron, 2008, 64, 4700) the preparation of 9 through oxidative degradation under the Windaus conditions only works with colchiceine (2) as a substrate but not with colchicine (1) itself.
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The mechanism originally proposed by Fernholz (ref. 8) is not compatible with our modern understanding of organic reactions, but even in the famous textbook of L. Fieser and M. Fieser (Organische Chemie, 2. Ed., Verlag Chemie, 1968) the colchicine-allocolchicine rearrangement is (erroneously) classified as a benzilic acid rearrangement.
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Long before the theory of electrocyclic reactions was introduced by Woodward and Hoffmann (giving the cycloheptatriene-norcaradiene interconversion as an example) the fragmentation of a norcaradiene intermediate related to 22 was suggested by W. Leimgruber, Dissertation ETH Zürich 1959, footnote on p. 33. We are very grateful to Prof. A. Eschenmoser for bringing this to our attention. Also, in their seminal paper on tropolone (ref. 20), Doering and Knox already considered norcaradienes (drawn as resonance structures) participating in such rearrangements
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