Synthesis of γ-Hydroxyalkyl Substituted Piperidine Iminosugars from d-Glucose

Abstract

D-Glucose was converted to synthetic equivalent of meso-pentodialdose, namely 3-C-(1'-aminoethyl)-alpha-d-ribo-pentodialdo-1,4-furanose 10 that gives an easy access to manipulate the aldehyde functionalities on either sides to get enantiomeric pair of 3. Thus, reduction of C5-aldehyde followed by hydrolysis of 1,2-acetonide functionality and reductive aminocyclization with C1-aldehyde afforded gamma-1,2-dihydroxyethyl piperidine iminosugar 3. On the other hand, first reductive aminocyclization with C5-aldehyde gave piperidine ring skeleton 12 that on removal of 1,2-acetonide and reduction of C1-aldehyde gave ent-3 while chopping of C1-aldehyde in 12 and reduction afforded gamma-hydroxymethyl piperidine iminosugar 4.

Synthesis of (2S,3R)-3-amino-2-hydroxydecanoic acid and its enantiomer: a non-proteinogenic amino acid segment of the linear pentapeptide microginin

“…The catalytic hydrogenation of alkene 4a with 10% Pd/C in methanol:ethyl acetate (3:2) at balloon pressure gave 4-heptyl-L-threose derivative 5a as a viscous oil in 99% yield [33]. Removal of the 1,2-acetonide group with TFA–water in 5a provided an anomeric mixture of the hemiacetal, which was directly subjected to oxidative cleavage by using sodium metaperiodate in acetone–water (to cleave the anomeric carbon) followed by a treatment with sodium borohydride to give triol 6a as a viscous oil in 78% overall yield in three steps [34]. The primary hydroxy group of triol 6a was selectively monosilylated with t -butyldiphenylsilyl chloride to give 7a .…”

C‐Branched Imino Sugars: Synthesis and Biological Relevance

“…The same reaction sequence as before afforded in turn the epimeric isofagomine derivative 40 . Dhavale and co‐workers also reported an elegant synthesis of compound 44 with an uncommon position for the characteristic geminal‐hydroxyhydroxymethyl feature (Scheme ) . Treatment of 3‐ulose 83 with allylzinc bromide allowed formation of the quaternary allylic alcohol 84 , .…”

1,2:5,6-Di-O-isopropylidene-3-C-methyl-α-D-allofuranose

“…For background information on this class of compound, see: Bio et al (2004); Canuto et al (2007); Mane et al (2008); Yoneda et al (2011). For details of ring-puckering calculations, see: Cremer & Pople (1975).…”

“…(2013). E69, o1512 The structural modification of carbohydrates has been extensively explored for improvement of their pharmacology properties (Bio et al, 2004;Canuto et al (2007); Mane et al 2008;Yoneda et al 2011). As ongoing research in developing potentially new drugs, we report here the structure of 1,2:5,6-Di-O-isopropylidene-3-C-methyl-α-D-allofuranose.…”