|Xu, Lin - UNIV OF ROCHESTER|
Submitted to: Carbohydrate Research
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: February 3, 2004
Publication Date: March 1, 2004
Citation: Xu, L., Price, N.P. 2004. Stereoselective synthesis of chirally-deuterated (S)-D-(6-**2H1]glucose. Carbohydrate Research. 339:1173-1178. Interpretive Summary: Biologically-active compounds from natural sources (natural products) are a major raw material source for pesticides, perfumes, favoring, etc. Understanding the biological routes by which they are made by plants and microbes is an important step towards producing new, high-value natural products. Historically, isotopically-labeled sugars have been invaluable to researchers for tracing these biosynthetic routes, although their preparation is generally expensive and often requires specialized apparatus. We have now successfully developed a novel method for the preparation of labeled glucose. Our innovation has been to use economical, commercially-available starting materials, and to optimize the yields at each step. The key step was achieved in 90% yield and, unlike previous work, does not require the preparation of expensive starting materials or the use of specialized apparatus. The work provides a valuable tool for researchers that will greatly impact our understanding of how natural products are made.
Technical Abstract: Chirally-deuterated D-(S)-[6-**2H1]glucose has been prepared in good overall yield from D-[6,6'-**2H2]glucose by a short step synthesis utilizing (R)-(+)-Alpine-Borane. Suitably protected methyl [6,6-**2H2]-2,3,4-tri-O-benzyl-D-glucopyranoside was prepared and the deuterated O-6 primary alcohol was oxidized to an aldehyde by Swern reaction. Stereoselective reduction with non-deuterated (R)-(+)-Alpine-Borane gave methyl 2,3,4-tri-O-benzyl-D-(6S)-[6-**2H1]glucopyranoside which was de-protected under standard conditions to afford the title compound. The key stereoselective reduction step was achieved in 90% yield. The preparation uses economical, commercially-available starting materials and will be useful for elucidating biosynthetic mechanisms.