Diastereoselective Entry to Novel Aminoindolizidines with Fused Furan, Thiophene, and Pyrrole Ring Starting from L‐Glutamic Acid

A series of novel optically pure aminoindolizidines featuring fused tetrahydro‐furan, thiophene, or pyrrole ring were synthesized from the proteinogenic L‐glutamic acid as a chiral precursor and a nitrogen atom source. The synthetic sequence employed tricyclic indolizidinols as advanced building blocks, which were prepared on a gram‐scale from bioavailable reagents. Key transformations within the used synthetic sequence included diastereoselective Thompson azidation, Staudinger reduction, Jurjew reaction, and highly diastereoselective catalytic hydrogenation. These steps facilitated the efficient and stereoselective synthesis of the ultimate amino‐ and N‐acetylamino‐indolizidines.