Modern Methods of Monosaccharide Synthesis from Non-Carbohydrate Sources

Department of Chemistry, University of Florida, Gainesville, Florida 32611.
Chemical Reviews (Impact Factor: 46.57). 06/1996; 96(3):1195-1220. DOI: 10.1021/cr9403300
Source: PubMed
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    ABSTRACT: The highly enantioselective Diels-Alder reaction between acryloyl oxazolidinone and furan, catalyzed by cationic bis(4-tert-butyloxazoline)Cu(II) complex 1, is presented. Though the reaction equilibrates rapidly at −20 °C, reaction at −78 °C permits isolation of the kinetic product mixture. The synthetic utility of the reaction is demonstrated by the conversion of the cycloadduct to ent-shikimic acid.
    Tetrahedron Letters 01/1997; 38(1):57-58. DOI:10.1016/S0040-4039(96)02259-9 · 2.38 Impact Factor
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    ABSTRACT: Aqueous aza Diels−Alder reactions of chiral aldehydes, prepared from carbohydrates, with benzylamine hydrochloride and cyclopentadiene, were promoted by lanthanide triflates. The exo/endo selectivities and diastereoselectivities of the reactions were elucidated by NMR, CD spectroscopy, and X-ray crystallography. The nitrogen-containing heterocyclic products were further transformed to azasugars, which are potential inhibitors against glycoprocessing enzymes.
    The Journal of Organic Chemistry 02/1997; 62(4). DOI:10.1021/jo962074s · 4.72 Impact Factor
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    ABSTRACT: Diisopropyl tartrate-modified (E)-[γ-(furyldimethylsilyl)allyl]boronates 10 and 11 were designed for the enantioselective synthesis of substituted anti-3,4-dihydroxy-1-butenes 9 via the anti-α-hydroxyallylation of aldehydes. The reactions of aldehydes with 10 and 11 provided furyldimethylsilyl-substituted anti-1,2-silanols 12 and 13 with good enantioselectivity (74−82% ee), and the silanols were oxidized to the corresponding anti-1,2-diols 9 by a modified Fleming−Tamao oxidation protocol. The high reactivity of the (menthofuryl)silane unit toward electrophilic substitution allowed complete protodesilylation of menthofuryl-substituted silanols 13 and subsequent oxidation to diols 9 in a one-pot operation without competing protodesilylation of the allylsilane unit. However, a two-step protocol was required for the protodesilylation−oxidation of the less reactive 2-(5-methyl)furyl-substituted silanols 12. Reagents 10 and 11 exhibited similar diastereoselectivity in double asymmetric reactions with three chiral aldehydes 23−25 (80 to >92% de, with the exception of the mismatched reactions with aldehyde 25, which were essentially unselective). However, [[[2-(5-methylfuryl)]dimethylsilyl]allyl]boronate 10 could only be synthesized in ≤15% yield, and oxidations of the 2-(5-methylfuryl)-substituted silanols 12 were lower-yielding than oxidations of the corresponding menthofuryl-substituted silanols 13. Thus, diisopropyl tartrate-modified (E)-[γ-[(menthofuryl)dimethylsilyl]allyl]boronate 11 proved to be the more useful of the two reagents. As a demonstration of the utility of 11 in the synthesis of polyhydroxylated natural products, this new reagent was used in a brief and highly stereoselective synthesis of the naturally occurring alkaloid (−)-swainsonine (42).
    The Journal of Organic Chemistry 02/1997; 62(4). DOI:10.1021/jo961840s · 4.72 Impact Factor
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