A Simple Route Toward New Clomiphene Metabolites

Abstract

A new clomiphene metabolite, extremely useful for doping analysis, was synthesized in 19% overall yield. The approach involved a Grignard reaction via a N-acylbenzotriazole intermediate to afford a key aromatic ketone and a HWE reaction. Both stereoisomers were separated and identified.

Synthesis and Antiradical Activity of Isoquercitrin Esters with Aromatic Acids and Their Homologues

“…When the aromatic OHs were protected by acetylation, the vinyl esters yielded with isoquercitrin (Novozym 435, 2 days, 45 °C) only undesired isoquercitrin 3″,6″-di- O -acetate (confirmed by MS and NMR). Using the benzyl-protected 4-hydroxybenzoic ( 26 ) [25], vanillic ( 27 ) [26], gallic ( 28 ) [27], p -coumaric ( 29 ), caffeic ( 30 ) [28] and ferulic ( 31 ) [29] acids, prepared according to the previous procedures (Figure 3, Section 2.2), enzymatic reactions (2 days, 45 °C) were also unsuccessful, in this case probably due to bulk acyl donors. Chemoenzymatic synthesis is therefore not completely versatile and IQ esters with aromatic acids 16 – 21 and therefore, their esters could not be prepared by this method.…”

“…Benzoic ( 12 ), phenylacetic ( 13 ), phenylpropanoic ( 14 ), cinnamic ( 15 ), 4-hydroxybenzoic ( 16 ), vanillic ( 17 ), gallic ( 18 ), p -coumaric ( 19 ), caffeic ( 20 ) and ferulic ( 21 ) acids, 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, antioxidant assay kit (CS0790); pooled microsomes from male rat liver (M9066); trolox and other chemicals were obtained from Sigma-Aldrich (Prague, Czech Republic). Vinyl esters ( 12 , 15 ) [22], ( 13 , 14 ) [23], and benzylated acids 16 [25], 17 [26], 18 [27], 19 , 20 [28], and 21 [29] were prepared as described previously.…”