New Building Block for Polyhydroxylated Piperidine: Total Synthesis of 1,6-Dideoxynojirimycin

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• 作者：Rajesh Rengasamy ; Marcus J. Curtis-Long ; Woo Duck Seo ; Seong Hun Jeong ; Ill-Yun Jeong ; Ki Hun Park
• 刊名：Journal of Organic Chemistry
• 出版年：2008
• 出版时间：April 4, 2008
• 年：2008
• 卷：73
• 期：7
• 页码：2898 - 2901
• 全文大小：87K
• 年卷期：v.73,no.7(April 4, 2008)
• ISSN：1520-6904

文摘

(3R,4S)-3-Hydroxy-4-N-allyl-N-Boc-amino-1-pentene 10, animportant precursor for the synthesis of polyhydroxylatedpiperidines, has been achieved as a single diastereomerwithout racemization via vinyl Grignard addition to N-Boc-N-allyl aminoaldehyde 9, which was derived from anenantiopure natural amino acid. Having forged a tetrahydropyridine ring scaffold 13 from 10 in 85% yield via RCMusing 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% overall yield) in excellent dr. To the best of our knowledge, oursynthesis of ent-1,6-dDNJ 1 is the most expeditious to date.