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19744368239
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note
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This is commercially available.
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50
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19744364646
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note
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The intermediates 16a,b correspond to the [4 + 2]-type and insertion mechanisms, respectively. See: ref 10.
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Pyridine 45 was previously prepared in 10 steps, in 8% overall yield, and as 96% ee from 1,1-dimethoxy-2-propanone. See: ref 14.
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Intermolecular double addition of acetylene-group 4 metal complexes to electrophilic carbon-heteroatom multiple bonds such as aldehydes, ketones, and imines is quite rare and is so far limited to a reactive acetylene complex such as that derived from enyne or an active electrophile represented by carbon dioxide: Hamada, T.; Mizojiri, R.; Urabe, H.; Sato, F. J. Am. Chem. Soc. 2000, 122, 7138-7139.
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α,α′-Dioxygenated pyrroles themselves recently attract interest in medicinal chemistry. Schweitzer, B. A.; Loida, P. J.; CaJacob, C. A.; Chott, R. C.; Collantes, E. M.; Hegde, S. G.; Mosier, P. D.; Profeta, S. Bioorg. Med. Chem. Lett. 2002, 12, 1743-1746.
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