Total synthesis of vineomycin B2

The first total synthesis of vineomycin B₂ (1) has been accomplished. The aglycon segment, a vineomycinone B₂ derivative, and the glycon segment, an α-l-acurosyl-l-rhodinose derivative, were prepared via C-glycosylation using an unprotected sugar and powerful chemoselective O-glycosylation using a 2,3-unsaturated sugar, respectively, as the key steps. Furthermore, effective and simultaneous introduction of the two glycon moieties to the aglycon part by concentration-controlled glycosylation led to the total synthesis of 1.