C‑4 Functional Group-Driven Stereodivergent Synthesis and Late-Stage Diversification of 6‑Deoxy l‑talo/gulo Rare Sugars

We
report a modular and stereodivergent synthesis of 6-deoxy-l-talose and 6-deoxy-l-gulose rare sugars via chemoselective glycosylation and regioselective dihydroxylation.
Judicious variation of the C-4 substitution precisely controlled diastereoselectivity,
enabling complementary access to both epimers. Proof-of-principle
and synthetic versatility were demonstrated with carbohydrates, amino
acids, natural products, and bioactive molecules, affording diverse
rare sugar analogs. Late-stage functionalization of custom-tailored
glycosides generated a library of rare sugar conjugates, including
ferrocene hybrids, medicinally valuable scaffolds, and therapeutic
agents.