Total synthesis of (+)-aplasmomycin

Enantiodivergent Transannular Rearrangement of 3‐Isopropyl‐1,4‐benzodiazepine‐2,5‐dione by Memory of Chirality

“…This can be related to the Chan reaction, [20] a base-induced rearrangement of an acyloxyacetate to a 2-hydroxy-3-oxo ester, and the N Ǟ C acyl migration of an acyclic imide, [21] two rare tools used in the total syntheses of aplasmomycin, [22] boromycin, [23] rapamycin, [24] diazonamide A [25] and taxol. [26] In order to explore this original reactivity, bis-Boc BZD 2 was subjected to other bases (Table 1).…”

Synthesis of Marine Natural Products with Antimalarial Activity

“…In a subsequent formal synthesis, Matsuda synthesized Corey's key intermediate 123 by connecting the two C(3)-C(11) and C(12)-C(17) segments, the latter based on asymmetric reduction of ketone 124 [130]. White used the same disconnection strategy proposed by Corey, but the intermediate 125 was prepared by using enatiomerically pure 126 from HPLC isolation [131].…”

Synthesis of the northern sector (C8–C19) of rapamycin via Chan rearrangement and oxidation of an α-acyloxyacetate

“…Our failure to acylate 43 with dimethyl oxalate caused us to revise our plan outlined in Scheme 1 for acquiring 3 and prompted us to consider a strategy used previously in our laboratory for assembling a similar structural motif to 3 present in the macrolides aplasmomycin21 and boromycin 22. Our new approach was based upon reorganization of an α-acyloxyacetate 52 to an α-hydroxy β-keto ester 53 (Scheme 9).…”