6-Su~fo-a-~-quinovopyranosyl phosphate was reacted with different nucleoside monophosphate morpholidates to form ADP-, CDP-, GDP-and UDP-sulfoquinovose. Analytical and preparative HPLC of these nucleotides was performed on reversed-phase columns using volatile buffer systems as eluant. The isolated compounds were characterized by NMR spectroscopy (except the CDP derivative) and used for an investigation of sulfolipid biosynthesis by chloroplasts. For this purpose intact spinach chloroplasts were biosynthetically preloaded with radioactive diacylglycerol to provide a sulfoquinovosyl acceptor. When sulfosugar nucleotides were added to such prelabelled intact organelles, the background levels of sulfolipid biosynthesis did not rise. On the other hand, after osmotic shock of prelabelled chloroplasts sulfolipid labelling was significantly increased by the addition of UDP-or GDP-sulfoquinovose. The same stimulation was observed with isolated envelope membranes, and UDP-sulfoquinovose proved to be twice as active as the GDP derivative. From these results it was concluded that the final step in sulfolipid biosynthesis is catalyzed by a UDP-sulfoquinovose: 1,2-diacylglycero13-0-a-D-sulfoquinovosyltransferase. This chloroplast enzyme cannot use exogenously supplied sulfosugar nucleotides, which as membrane-impermeable compounds are expected to be formed in viwo within chloroplasts.The plant sulfolipid 1 ',2'-di-0-acyl-3'-0-(6-deoxy-6-sulfoa-D-glucopyranosy1)-sn-glycerol [I] is a membrane lipid found in higher plants, cyanobacteria and some other photosynthetic procaryotes [2]. With regard to the sulfur budget of plants, the sulfolipid represents a major component which accounts for about half of the organic sulfur in leaves [3]. In higher plants this unique glycolipid is confined to plastids [4]. In these organelles it is located in the two surrounding envelopes as well as in the inner thylakoid membranes [5], where part of it may be firmly bound to specific protein complexes [6 -81.After application of radioactive sulfate to plants, the sulfolipid is rapidly labelled [I, 2, 91. Despite this specific and easy labelling, several steps in sulfolipid biosynthesis have not been resolved and at present two alternative routes are discussed. It has been suggested that a sulfoglycolytic sequencc [lo -121 produces 3-sulfo-~-lactaldehyde which instead of 3-phospho-~-glyceraldehyde can be used by aldolase [lo] to form 6-deoxy-6-sulfo-~-fructofuranosyl 1-phosphate. Subsequent hydrolysis and isomerisation to 6-sulfoquinovose (quinovose = 6-deoxy-~-glucose), rephosphorylation at C-I and activation by a corresponding pyrophosphorylase could result in a nucleoside diphospho-sulfoquinovose. Such a com-
Performing regioselective alkylation at 3′‐OH of benzyl β‐lactoside 1 by the stannylation method we prepared the 3′‐OH‐ and 4′‐OH‐unprotected lactose derivatives 5 and 10 and the 4′‐OH‐unprotected lactose derivative 9 containing a different protecting group at 3′‐OH, suitable for further transformations. These building blocks are valuable glycosyl acceptors in glycolipid synthesis. For the synthesis of glycosyl donors with Gal(β1 → 4)GlcNAc‐structure we used the 2‐azido lactose derivative 19. By regioselective alkylation of 3′‐OH by the stannylation method and application of other common regioselective protecting procedures we prepared the trichloroacetimidates 17, 24, and 30 containing special protecting groups at 3′‐OH, 4′‐OH, and 6′‐OH which are suitable for further transformations in these positions.
Treatment of glycopyranosyl phenyl sulfoxides 2ah, 1, 2bh, 1 with two equivalents of lithium diisopropylamide provides directly the C‐2‐lithiated glycal intermediates 3aAh, 1, 3bAh, 1 which, on reaction with formaldehyde as electrophile, furnish the 2‐hydroxymethyl derivatives 4ah, 1 and 4bh, 1, respectively. These compounds are transformed at elevated temperature and by acid catalysis directly into the α‐methylene‐δ‐lactones 5a, b. Correspondingly, from 2ah, 1 and methyl chloroformate as electrophile the 2‐methoxycarbonyl derivatives 6h and 61, respectively, are obtained. Treatment of 6h, 1 with Raney nickel leads to 2‐methoxycarbonyl‐substituted glycal 7 containing a β‐alkoxyacrylate moiety which again can be directly β‐C‐lithiated as demonstrated by the introduction of deuterium at C‐1.
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