Total Synthesis of an Immunomodulatory Phosphoglycolipid from Thermophilic Bacteria

Lin, Hong-Jyune; Adak, Asok; Reddy, L. Vijaya Raghava; Wu, Shih‐Hsiung; Lin, Chun‐Cheng

doi:10.1002/chem.201204550

Cited by 8 publications

(11 citation statements)

References 75 publications

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“…The next step in the synthesis was the conversion of commercially available 1‐palmitoyl‐2‐oleoyl‐ sn ‐glycerol to the phosphoramidite needed to couple to cholesteryl glucose. This was achieved by first activating 2‐cyanoethyl N , N , N ,′ N ′‐tetraisopropylphosphordiamidite with tetrazole and its displacement with 1‐palmitoyl‐2‐oleoyl‐ sn ‐glycerol 6 to afford the phosphoramidite 14 in 92 % yield as a 1:1 mixture of diastereomers (Scheme ) 12. The same strategy was utilized to prepare phosphoramidite 13 from 5 11a and 15 from 12 (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Structural Characterization of Three Unique Helicobacter pylori α‐Cholesteryl Phosphatidyl Glucosides

2014

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Steryl glycosides produced by bacteria play important biological roles in the evasion and modulation of host immunity. Step‐economical syntheses of three cholesteryl‐6‐O‐phosphatidyl‐α‐D‐glucopyranosides (αCPG) unique to Helicobacter pylori have been achieved. The approach relies upon regioselective deprotection of per‐O‐trimethylsilyl‐α‐D‐cholesterylglucoside at C6 followed by phosphoramidite coupling. Global TMS ether deprotection in the presence of oxygen and subsequent deprotection of the cyano ethyl phosphoester afforded the target compounds in 16–21 % overall yield starting from D‐glucose. The structures of these natural products were determined using a combination of 2D NMR methods and mass spectrometry. These robust synthesis and characterization protocols provide analogues to facilitate glycolipidomic profiling and biological studies.

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Section: Methodsmentioning

confidence: 99%

Synthesis and Structural Characterization of Three Unique Helicobacter pylori α‐Cholesteryl Phosphatidyl Glucosides

2014

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“…This process revealed the constituent phospholipids of C. calidirosea included the two previously reported lipids (T49-E, 10 and -M, 11) and three analogous structures bearing an αlinked glucose (T49-Q, 12) xylose (T49-L, 13) and N-alanylglucosamine (T49-O, 14). For the first time, an analogous series of phospholipids to those reported above, each bearing an oxygenated alkylamine chain (15)(16)(17)(18)(19) (Table 1), are also described.…”

Section: Isolation and Identification Of C Calidirosea Phospholipidsmentioning

confidence: 99%

“…In the case of 10, peracetylation showed addition of one extra acetyl group (relative to 10) confirming the alkylamine moiety contains a free hydroxyl functionality. The low abundance of minor satellite compounds in some pairs did not permit full structural elucidation, however, the major lipids T49-M3 (16) and T49-O3 (19) were isolated in quantities which allowed for additional NMR experiments (SI Figure 14). These established the location of the extra oxygen in fatty amine chain at C-3 however the absolute stereochemistry about this OH group could not be ascertained in this study.…”

Section: Entrymentioning

confidence: 99%

Isolation and Synthesis of Glycophospholipids from the extremophile Chthonomonas calidirosea

et al. 2020

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An interesting set of ten phospholipids including eight previously unreported compounds have been isolated from the extremophile Chthonomonas calidirosea (strain T49 T). Common within these metabolites is the phosphatidylglyceroylalkylamine core unit with the newly identified compounds containing α-linked glucosyl, xylosyl or Nalanylglucosaminyl monosaccharides. The previously reported N-acetylglucosaminyl and aglycone derivatives were also identified in extracts from this bacterium. All metabolites were accompanied by a structural isomer which was shown to contain an extra hydroxyl group within the alkylamine chain. The absolute regio-and stereochemistries of the major phospholipids were confirmed by total synthesis.

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“…Recently, Lin used N‐ benzyl 2,3‐ trans ‐carbamate‐type donors for the synthesis of immunomodulatory phosphoglycolipids isolated from thermophilic bacteria …”

Section: 2‐cis Aminoglycoside Formation Using Glycosyl Donors Withmentioning

confidence: 99%

Pyranosides with 2,3‐trans Carbamate Groups: Exocyclic or Endocyclic Cleavage Reaction?

Manabe

Ito

2014

The Chemical Record

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Pyranosides with 2,3-trans carbamate groups exhibit high 1,2-cis selectivity in glycosylation reactions. Using glycosyl donors with N-benzyl 2,3-trans carbamate groups, an anti-Helicobacter pylori oligosaccharide was synthesized in an efficient manner. Moreover, pyranosides with 2,3-trans carbamate groups readily undergo anomerization from the β to the α configuration under mild acidic conditions via endocyclic cleavage. Acyclic cations generated during the endocyclic cleavage reaction were captured using reduction and intramolecular Friedel-Crafts reaction. By exploiting this anomerization, multiply aligned 1,2-trans glycosyl bonds can be transformed to 1,2-cis glycosyl bonds in a single operation.

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Total Synthesis of an Immunomodulatory Phosphoglycolipid from Thermophilic Bacteria

Cited by 8 publications

References 75 publications

Synthesis and Structural Characterization of Three Unique Helicobacter pylori α‐Cholesteryl Phosphatidyl Glucosides

Synthesis and Structural Characterization of Three Unique Helicobacter pylori α‐Cholesteryl Phosphatidyl Glucosides

Isolation and Synthesis of Glycophospholipids from the extremophile Chthonomonas calidirosea

Pyranosides with 2,3‐trans Carbamate Groups: Exocyclic or Endocyclic Cleavage Reaction?

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