Total Syntheses of Dendrodolides A, B, and E

Convergent total syntheses of dendrodolides A, B, and E comprising 12‐membered macrolactones are described. The syntheses of dendrodolides A and B were accomplished in 11 linear steps with 24 % and 25 % overall yield, respectively, starting from commercially available homoallyl alcohol 19 and enantiomerically pure epoxide 20. Dendrodolide E was subsequently obtained from dendrodolides A or B in 81 % yield by treatment with BCl3. Key steps were Maruoka asymmetric allylation, Corey‐Chaykovsky reaction, Yamaguchi esterification, and ring‐closing metathesis. Chemist's XI: Efficient stereoselective total syntheses of dendrodolides A and B have been accomplished in 11 linear steps with 24 % and 25 % overall yield, respectively, starting from a commercially available homoallyl alcohol. Dendrodolide E was subsequently obtained from dendrodolides A or B in 81 % yield by treatment with BCl3. Bn=benzyl: PMB=para‐methoxybenzyl; RCM=ring‐closing metathesis.