Stereoselective synthesis of (+)-diplodialides-B, C and a formal synthesis of (+)-diplodialide-A by ring-closing metathesis approach

Stereoselective synthesis of diplodialides-B and C and the formal synthesis of diplodialide-A are reported. A combination of Jacobsen’s hydrolytic kinetic resolution and Sharpless epoxidation is used for the creation of two stereogenic centers, while a ring-closing metathesis strategy was used for the construction of the lactone ring.

Graphical abstractSynthesis of compounds 2 and 3 is described, along with the formal synthesis of 1.Figure optionsDownload full-size imageDownload as PowerPoint slide

(4S,10R)-4-Hydroxy-10-methyl-3,4,7,8,9,10-hexahydro-2H-2-oxecinoneC10H16O3[α]D = −35.8 (c 0.2, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (4S,10R)

(4R,10R)-4-Hydroxy-10-methyloxecan-2-oneC10H18O3[α]D = −39.7 (c 0.25, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (4R,10R)