[reaction: see text] Using a chemoenzymatic synthetic strategy, (S)-imperanene and its (R)-enantiomer has been synthesized from vanillin in nine steps. The key step in the synthesis involves the use of Pseudomonas cepacia lipase (PS-30) to induce asymmetrization of the intermediary prochiral 1,3-diol in >97% ee.
Chemoenzymatic synthesis and modification of well-defined macrolactonic sophorolipid (SLML) analogues via a series of successive regioselective de-esterification/transesterification reactions is investigated. Of the lipases screened, Candida antartica lipase-B (Novozyme-435) successfully deacylated the C-6′ acetoxy group of natural and peracylated SLMLs. Subsequent transesterification with acylating agents (esters of fatty acids) was successful only with the C-6′ deacetylated natural SLML providing an avenue to well-defined analogues of varying amphilicity. The macrolactonic motif was essential for enzymatic recognition of the sophorose rings of these complex glycolipids. In the absence of the lactonic motif, the peracylated sophorose rings are not deacylated, rather the carboxyl end of the non-lactonic forms that was preferentially transesterified. All macrolactonic derivatives were characterized by IR, 1 H, 13 C, 1 H-1 H and 1 H-13 C NMR spectroscopy, as well as HRMS where applicable.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.