New building block for polyhydroxylated piperidine: total synthesis of 1,6-dideoxynojirimycin.
(3R,4S)-3-Hydroxy-4-N-allyl-N-Boc-amino-1-pentene 10, an important precursor for the synthesis of polyhydroxylated piperidines, has been achieved as a single diastereomer without racemization via vinyl Grignard addition to N-Boc-N-allyl aminoaldehyde 9, which was derived from an enantiopure natural amino acid. Having forged a tetrahydropyridine ring scaffold 13 from 10 in 85% yield via RCM using Grubbs II catalyst, we were able to effect its stereodivergent dihydroxylation, via a common epoxide intermediate to yield a range of interesting hydroxylated piperidines, including ent-1,6-dideoxynojirimycin (ent-1,6-dDNJ) 1 (28% overall yield) and 5-amino-1,5,6-trideoxyaltrose 2 (29% over all yield) in excellent dr. To the best of our knowledge, our synthesis of ent-1,6-dDNJ 1 is the most expeditious to date.
Rengasamy
Rajesh
R
Division of Applied Life Science (BK21 program), EB-NCRC, Gyeongsang National University, Jinju 660-701, South Korea.
Curtis-Long
Marcus J
MJ
Seo
Woo Duck
WD
Jeong
Seong Hun
SH
Jeong
Ill-Yun
IY
Park
Ki Hun
KH
D017485:1-Deoxynojirimycin / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D006900:Hydroxylation; D008968:Molecular Conformation; D010880:Piperidines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
C513752:1,6-dideoxynojirimycin; D010880:Piperidines; D017485:1-Deoxynojirimycin