191 research outputs found

    Straightforward Synthesis of α,β-Unsaturated Thioesters via Ruthenium-Catalyzed Olefin Cross-Metathesis with Thioacrylate

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    The cross-metathesis reaction of S-ethyl thioacrylate with a variety of olefins is effectively catalyzed by using a ruthenium benzylidene olefin metathesis catalyst. This reaction provides a convenient and versatile route to substituted α,β-unsaturated thioesters, key building blocks in organic synthesis.

    Racemic Total Synthesis of Elmonin and Pratenone A, from Streptomyces, Using a Common Intermediate Prepared by peri-Directed C-H Functionalization

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    [Image: see text] The first total synthesis of elmonin and pratenone A, two complex rearranged angucyclinones from Streptomyces, is reported. Using peri-directed C–H functionalization, the key naphthalene fragment present in both synthetic targets was efficiently prepared. Coupling to two anisole-derived fragments gave access to the natural products, in which elmonin was prepared using a biomimetic spiro-ketalization

    Synthesis of phosphatidic acids via cobalt(salen) catalyzed epoxide ring-opening with dibenzyl phosphate

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    With a CoIII(salen)OTs catalyst, dibenzyl phosphate ring-opens a variety of terminal epoxides with excellent regio-selectively and yields up to 85%. The reaction is used in a highly efficient synthesis of enantiopure mixed-diacyl phosphatidic acids, including a photoswitchable phosphatidic acid mimic

    Site-selective introduction of thiols in unprotected glycosides

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    Thioglycosides or S-linked-glycosides are important glycomimetics. These thioglycosides are often prepared by glycosylating deoxythio sugar acceptors, which are synthesized via elaborate protecting group manipulations. We discovered that a carbonyl group, formed by site-selective oxidation of unprotected saccharides, can be converted into a thiol moiety. The transformation involves SN1-substitution of a chloro-azo intermediate, formed by oxidation of the corresponding trityl hydrazone, with a thiol. The prepared deoxythio sugars provide, in combination with the recently developed protecting group-free glycosylation of glycosyl fluorides, a protecting group-free synthesis of thioglycosides.</p

    From d- to l-Monosaccharide Derivatives via Photodecarboxylation-Alkylation

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    Photodecarboxylation-alkylation of conformationally locked monosaccharides leads to inversion of stereochemistry at C5. This allows the synthesis of l-sugars from their readily available d-counterparts. Via this strategy, methyl l-guloside was synthesized from methyl d-mannoside in 21% yield over six steps

    Chiral separation by enantioselective liquid–liquid extraction

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    The literature on enantioselective liquid–liquid extraction (ELLE) spans more than half a century of research. Nonetheless, a comprehensive overview has not appeared during the past few decades. Enantioselective liquid–liquid extraction is a technology of interest for a wide range of chemists and chemical engineers in the fields of fine chemicals, pharmaceuticals, agrochemicals, fragrances and foods. In this review the principles and advances of resolution through enantioselective liquid–liquid extraction are discussed, starting with an introduction on the principles of enantioselective liquid–liquid extraction including host–guest chemistry, extraction and phase transfer mechanisms, and multistage liquid–liquid extraction processing. Then the literature on enantioselective liquid–liquid extraction systems is reviewed, structured on extractant classes. The following extractant classes are considered: crown ether based extractants, metal complexes and metalloids, extractants based on tartrates, and a final section with all other types of chiral extractants.

    Characterization of Mycobacterium tuberculosis Mycolic Acids by Multiple-Stage Linear Ion-Trap Mass Spectrometry

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    Mycobacterium tuberculosis (Mtb) cells are known to synthesize very long chain (C60-90) structurally complex mycolic acids with various functional groups. In this study, we applied linear ion-trap (LIT) multiple-stage mass spectrometry (MSn), combined with high-resolution mass spectrometry to study the mechanisms underlying the fragmentation processes of mycolic acid standards desorbed as lithiated adduct ions by ESI. This is followed by structural characterization of a Mtb mycolic acid family (Bovine strain). Using the insight fragmentation processes gained from the study, we are able to achieve a near complete characterization of the whole mycolic acid family, revealing the identity of the α-alkyl chain, the location of the functional groups including methyl, methoxy, and keto groups along the meroaldehyde chain in each lipid species. This study showcased the power of LIT MSn toward structural determination of complex lipids in a mixture, which would be otherwise very difficult to define using other analytical techniques

    Novel compositions and methods for trehalose phospholipids

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    Provided herein are compositions of trehalose phospholipids and uses thereof, e.g., compounds and compositions comprising 6,6'-diphosphatidyltrehalose (diPT) and analogs thereof with modifications of the diPT chemical scaffold, that bind and agonize Mincle, and the use thereof as adjuvants
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