37. A New Total Synthesis of dl-Pumiliotoxin-C via an Indanone
    Oppolzer, W.; Fehr, C.; Warneke, J.
    Helv. Chim. Acta 1977, 60, 48-58

dl-Pumiliotoxin-C (4) was synthesized in a practical manner from trans-4-hexenal (9). The key step 14 → 15 (Scheme 3) involves an intramolecular Diels-Alder reaction giving mainly the cis-fused indanols 15a, which were converted to the cis-fused ketone 16. AfterBeckmann-rearrangement of 16 the octahydroquinolinone 7 was transformed to the lactim-ether 23. (Scheme 7). Reaction of 23 with propylmagnesium bromide followed by hydrogenation furnished dl-4 in a highly stereoselective fashion.

DOI : 10.1002/hlca.19770600108