Synthesis of Vicinal Diketoses by Using a Metathesis–Hydroxylation–Oxidation Sequence. Issue 34 (24th October 2014)

• Record Type: Journal Article
• Authors: Menzel, Melchior; Ziegler, Thomas
• Is Part Of: European journal of organic chemistry. Issue 34(2014)
• Page Start: 7658
• Page End: 7663
• Publication Date: 2014-10-24
• Subjects: Carbohydrates -- Metathesis -- Dihydroxylation -- Oxidation -- Configuration determination; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201403140
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: Symmetrical vicinal diuloses were prepared from 2, 3:4, 5‐di‐ O ‐isopropylidene‐D ‐arabinose and ‐L ‐arabinose by using methyltriphenylphosphonium bromide to convert both enantiomers into the corresponding 1, 2‐dideoxy‐3, 4:5, 6‐di‐ O ‐isopropylidene‐ arabino ‐hex‐1‐enitolsD‐5 andL‐5 . The metathesis reactions ofD‐5 with itself and withL‐5, respectively, by using the Hoveyda–Grubbs catalyst gave diastereomeric dec‐5‐enitolsDD‐6 andDL‐6, which were dihydroxylated with osmium tetroxide to give 1, 2:3, 4:7, 8:9, 10‐tetra‐ O ‐isopropylidene‐protected decitolsDD‐7 andDL‐7 . Swern oxidation of the decitols afforded isopropylidene‐protected deco‐5, 6‐diulosesDD‐8 andDL‐8, which gave unprotected deco‐5, 6‐diulosesDD‐9 andDL‐9 upon acidic cleavage of the isopropylidene groups. The structures of both diastereomers were confirmed by NMR spectroscopy and X‐ray crystal structure analysis. Abstract : The attempted structure elucidation and total synthesis of a naturally occurring antidiabetic drug led to the synthesis of two higher monosaccharides by using an olefination, cross‐coupling, and oxidation reaction sequence. This synthetic strategy paves the way to a new class of substances that is not yet well investigated.