Enamino ester reduction: A short enantioselective route to pyrrolizidine and indolizidine alkaloids. Synthesis of (+)-laburnine, (+)-tashiromine, and(-)-isoretronecanol
O. David et al., Enamino ester reduction: A short enantioselective route to pyrrolizidine and indolizidine alkaloids. Synthesis of (+)-laburnine, (+)-tashiromine, and(-)-isoretronecanol, J ORG CHEM, 64(9), 1999, pp. 3122-3131
Various chiral pyrrolidine tetrasubstituted beta-enamino esters were reduce
d catalytically or chemically with good to moderate diastereoselectivity ow
ing to a chiral induction originated from (S)-alpha-methylbenzylamine. With
endocyclic double bond compounds, the best result was obtained using PtO2
as hydrogenation catalyst and led to a major syn addition product (e.d. 90%
). In the case of exocyclic double bond compounds, hydrogenation over Pd/C
gave rise to the higher diastereoselectivity and mainly afforded the unexpe
cted anti addition product (e.d. 84%). The scope of these reductions has be
en extended to the synthesis of three pyrrolizidine or indolizidine alkaloi
ds: (+)-tashiromine, (+)-laburnine, and (-)-isoretronecanol. Syntheses of t
hese natural products, starting from chiral beta-enamino diesters, were ach
ieved in a short and convenient manner, leading to enantiopure compounds in
good overall yields.