Abstract
The first synthesis of four new naturally occurring remotely functionalized secondary mould metabolite anhydrides 1a -d is described starting from N -p -tolyl citraconimide (5 ) in three to six steps and 20-65% overall yields. The condensation of triphenylphosphine-maleimide adduct 6 with aldehyde 4 furnished the exo -imide 7 , which after isomerization, hydrolysis, and acylation gave aspergillus acid A (1a ) in 54% overall yield in four steps. The condensation of adduct 6 with aldehyde 15 similarly afforded the desired imide 17 in two steps. The acid-catalyzed hydrolysis of imide 17 directly furnished aspergillus acid B (1b ), exposing the latent methyl ketone present as the terminal acetylene. Sodium borohydride induced chemoselective reduction of aspergillus acid B (1b ) gave aspergillus acid C (1c ), which upon acetic anhydride induced acylation, furnished aspergillus acid D (1d ). A facile Amano PS catalyzed acylation of aspergillus acid C (1c ) gave, in good yield, the desired (+)-aspergillus acid C (1e ) in 70% ee and (-)-aspergillus acid D (1f ) in 72% ee. In the present enzymatic reaction, the anhydride moiety presumably plays a crucial role in the substrate recognition, binding, and resolution process.
Key words
citraconimide - Wittig condensation - chemoselective reduction - aspergillus acid - enzymatic resolution
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