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8
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Most publications describe indolizidines 167B and 209D as natural. However, according to Daly's recent reviews, the two isolated natural alkaloids (proposed tentatively to be indolizidines 167B and 209D) were found to be 3,5-disubstituted pyrrolizidines and were, therefore, tabulated as indolizidines 167F and 209K in the appendix. The code names 167B and 209D are maintained for the synthetic indolizidines, although they have not yet been detected in nature. Please see: J.W. Daly, T.F. Spande, and H.M. Garraffo J. Nat. Prod. 68 2005 1556
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R.S. Aronstam, J.W. Daly, T.F. Spande, T.K. Narayanan, and E.X. Albuquerque Neurochem. Res. 11 1986 1227
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For the first asymmetric total synthesis of indolizidine 167B and 209D see: R.P. Polniaszek, and S.E. Belmont J. Org. Chem. 55 1990 4688
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For recent examples of the asymmetric synthesis of indolizidine 167B and 209D see: R. Lazzaroni, and R. Settambolo Chirality 23 2011 730
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Although no example of the photochemical Wolff rearrangement applied to the Arndt-Eistert reaction is described in the literature for an α,β-unsaturated diazoketone, a single example is described for the thermal rearrangement by Brueckner. However, the 2 diazoketones employed in this example are simple ones, containing no epimerizable stereocenters or heteroatoms in the chain. For this single example, see: T. Kapferer, R. Brueckner, A. Herzig, and W.A. Koenig Chem. Eur. J. 11 2005 2154
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