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We report the app
lication of peptide-embedded imidazo
les as cata
lysts for the site-se
lective de
livery ofthe pheny
l thionoformate unit as a pre
lude to deoxygenation reactions of po
lyo
ls. Methodo
logy wasdeve
loped that a
llows for the synthesis of thiocarbony
l derivatives based on a combination of additivesthat inc
lude
N-a
lky
limidazo
les and FeC
l3 as co-cata
lysts. The use of this reagent combination
leads toincreased reaction rates and efficient yie
lds re
lative to those of
simp
le base-mediated reactions. In termsof contro
lling regiose
lectivity during the course of po
lyo
l modification, we found that histidine-containingpeptides, in combination with FeC
l3, cou
ld
lead to modu
lation of the product distribution. Throughscreening of peptides and contro
l of reaction conditions, products cou
ld be observed that ref
lected boththe inherent preference of substrates and a
lso reversa
l of inherent se
lectivity.