A catalytic asymmetric total synthesis of (−)-perophoramidine

Abstract

We describe a catalytic asymmetric total synthesis of the ascidian alkaloid (–)-perophoramidine employing a Mo-catalyzed asymmetric allylic alkylation and unprecedented imino ether allylation as key steps.

A Divergent Synthetic Route to the Vallesamidine and Schizozygine Alkaloids: Total Synthesis of (+)‐Vallesamidine and (+)‐14,15‐Dehydrostrempeliopine

“…The oxidative cleavage of the allyl group in 18 was initially problematic either by ozonolysis or under OsO 4 /NaIO 4 conditions, probably owing to the oxidation‐sensitive piperidine nitrogen atom. Protonation of the basic piperidine nitrogen atom with TFA acted as in situ protection, and upon ozonolysis smoothly gave the aldehyde in 90 % yield . In preparation for the late‐stage ring‐closing metathesis to form ring D, the PMB group had to be removed and changed to an allyl group.…”

Applications of Mitsunobu Reaction in total synthesis of natural products

“…Perophoramidine and Communesin F as two structurally related alkaloids bearing indole moiety was initially isolated from marine types Perophora namei and Enteromorpha intestinalis , respectively . In this line, perophoramidine was screened for possible biological activity which showed high potency towards the HCT116 colon cancer cells.…”

“…[222] The latter was subjected to classical Mitsunobu conditions [227] providing methyl ether 167, regioselectively compound 167 was transformed into ester 168 after several steps (76% yield) The latter was then converted to the desired natural product 164 via multi-step synthesis (Scheme 33). Perophoramidine [228,229] and Communesin F [230,231] as two structurally related alkaloids bearing indole moiety was initially isolated from marine types Perophora namei and Enteromorpha intestinalis, respectively. [232] In this line, perophoramidine was screened for possible biological activity which showed high potency towards the HCT116 colon cancer cells.…”

Recent Advances on the Total Syntheses of Communesin Alkaloids and Perophoramidine

“…53 Unlike many other syntheses, which utilized a [4+2]-cycloaddition as their key step, the Trost group developed a route to this natural product utilizing a Mo-catalyzed asymmetric allylic alkylation (Mo-AAA) as the key enantiodetermining process. The synthesis commenced with the preparation of the two Mo-AAA coupling partners (Scheme 51).…”