Convergent, enantiospecific total synthesis of the novel cyclodepsipeptide (+)-jasplakinolide (jaspamide)

Abstract

Jasplakinolide (l),2 a novel cyclodepsipeptide isolated from a soft-bodied sponge, Jaspis sp., contains a new amino acid, 2-OH bromoabrine, possessing the unnatural D configuration and the rare amino acid (J?)-jS-tyrosine.3The potent insecticidal, antifungal, and anthelminthic properties2 of jasplakinolide have been responsible for considerable synthetic activity in both industrial and academic laboratories.We wish to record the first total synthesis of (+)-jasplakinolide.The approach detailed below is both highly convergent and enantiospecific.Our strategy for elaboration of jasplakinolide centered around the coupling of dipeptide 2 with the L-alanine derived acyclic fragment 3. Construction of dipeptide 2 necessitated prior de- velopment of synthetic routes to the unnatural amino acids, (J?)-0-tyrosine and D-bromoabrine.