Amino-Acetone-Bridged Cyclodextrins - Artificial Alcohol Oxidases

作者：Marinescu Lavinia G^*; Doyaguez Elisa G; Petrillo Marta; Fernandez Mayoralas Alfonso; Bols Mikael

来源：European Journal of Organic Chemistry, 2010, 2010(1): 157-167.

DOI：10.1002/ejoc.200901099

• Airlines
• Enzyme catalysis
• Alcohols
• Oxidation
• Cyclodextrins

A new series of alpha- and beta-cyclodextrin derivatives containing a substituted amino-acetone bridge attached to the 6A and 6D positions of the cyclodextrin are reported. The synthesis starts from the known alpha- or beta-cyclodextrin A,D-diols, which were either oxidized to alpha- or beta-cyclodextrin A,D-dicarbal-dehydes and then coupled with 1,3-diamino-2-propanol by a reductive amination reaction and further modified to give the final 6(A),6(D)-diamino-6(A),6(D)-dideoxy-N,N'-(2-oxopropa-1,3-dienyl)-N,N'-acetyl-alpha- or -beta-cyclodextrin or the cyclodextrindiol was substituted with azide then reduced and after a few alkylation steps the final 6(A),6(D)-dideoxy-N,N'-(2-oxopropa-1,3-dienyl)-6(A),6(D)-(N,N,N'N'-tetramethyldiammonio)-alpha-cyclodextrin dibromide was obtained. The new compounds display very good enzymatic catalytic properties in the oxidation of benzyl alcohols with a rate increase of up to 18500 but only appreciable catalysis for aniline oxidations. Thus, unlike previously studied cyclodextrin ketones, these new amino-acetone-bridged cyclodextrins have high substrate selectivity and also exhibit stereoselectivity in the oxidation of different enantiomers.

• 出版日期2010-1