Naturally occurring polyhydroxylated amines such as (+)-1-deoxynojirimycin, polyoxamic acid, anisomycin, (−)swainsonine, and alexine stereoisomers, which have interesting biological activities including glucosidase- and mannosidase-inhibitory activity, immunoregulatory activity, and antibacterial effects, were synthesized stereoselectively starting from (
S)-pyroglutamic acid derivatives. α,β-Unsaturated lactams ((
S)-5-hydroxymethyl-2-oxo-3-pyrroline derivatives), α,β-unsaturated δ-lactone ((
S)-4-amino-2-penten-5-olide derivative), and
E-olefin ((
S,
E)-methyl-4-amino-5-hydroxypent-2-enoate derivative) from (
S)-pyroglutamic acid derivatives were dihydroxylated using OsO
4 in the presence of
N-methyl morpholine
N-oxide (NMO) to afford various chiral building blocks with different configurations. The stereoselectivity of
cis-dihydroxylation for α,β-unsaturated lactams and α,β-unsaturated δ-lactone was very high, while the stereoselectivity was low for
E-olefin. Therefore, the double asymmetric induction of
E-olefin using K
2OsO
4 with chiral ligands was successively applied to yield high stereoselectivity. (2
R,3
S)-2-Hydroxymethyl-3-hydroxypyrrolidine and Gaissman-Weiss lactone, important intermediates for the preparation of pyrrolizidine alkaloids, were synthesized from a (3
R,4
R,5
R)-3,4-dihydroxy-5-hydroxymethyl-2-pyrrolidinone derivative derived from α,β-unsatulated lactam. (+)-1-Deoxynojirimycin was synthesized from a (2
S,3
R,4
R)-methyl 4-amino-2,3,5-trihydroxypentanoate derivative of
E-olefin. (−)-Swainsonine and its stereoisomers were synthesized from (2
R,3
S,4
R)- or (2
R,3
R,4
R)-2-hydroxymethyl-3,4-dihydroxypyrrolidine derivatives of α,β-unsaturated δ-lactone or α,β-unsaturated lactam. The key reaction was diastereoselective allylation of the aldehyde derived from the corresponding 2-hydroxymethylpyrrolidine derivatives with various allylation reagents. The high diastereoselectivity could be explained by cyclic chelate formation between metals and the α-aminocarbonyl group or β-alkoxycarbonyl group, in which the nucleophile approaches from the less hindered face. Four alexine stereoisomers were synthesized from (2
R,3
R,4
S,5
R)- and (2
R,3
R,4
S,5
S)-2,3-dihydroxymethyl-3,4-dihydroxyl pyrrolidine derivatives of α,β-unsaturated lactam.
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