One-step labelling of sphingolipids via a scrambling cross-metathesis reaction

Nußbaumer, Peter; Ettmayer, Peter; Peters, Carsten; Rosenbeiger, Daniela; Högenauer, Klemens

doi:10.1039/b508132g

Cited by 29 publications

(14 citation statements)

References 14 publications

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“…[5,9,10] Opting for a short and easily reproducible route, we used a method which we recently described for efficient synthesis of backbone-labeled sphingolipids. [7,11] Olefin cross metathesis of allyl alocohol 4 [12] and N-Boc-undec-10-enylamine (5) [13] under standard conditions using Grubb's catalyst (2nd generation) gave 6 in excellent yields (Scheme 1) under exclusive formation of the (E)-double bond, as previously observed with similar analogues by us [7,11] and others. [14] The secondary alcohol was protected as tert-butyl-diphenylsilyl (TBDPS) ether prior to cleavage of the acetonide by aqueous acetic acid [15] to afford 7.…”

Section: Resultssupporting

confidence: 61%

Synthesis and Immobilization of erythro‐C14‐ω‐Aminosphingosine‐1‐phosphate as a Potential Tool for Affinity Chromatography

et al. 2008

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A sphingosine-1-phosphate (S1P) analogue containing a terminal alkyl chain amino group is synthesized in a few steps via olefin cross-metathesis of an optically resolved intermediate and subsequent phosphorylation. Regioselective acylation of this intermediate at its N terminus in solution is demonstrated as a model reaction and provides a biologically active derivative. Finally, the omega-amino intermediate is immobilized on an affinity matrix. The choice of a UV-active phosphate protecting group allows for quantification of resin loading after cleavage which amounted to 66 %.

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Section: Resultssupporting

confidence: 61%

Synthesis and Immobilization of erythro‐C14‐ω‐Aminosphingosine‐1‐phosphate as a Potential Tool for Affinity Chromatography

et al. 2008

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“…However, it has been noted45,51 that the cross-metathesis products are formed almost exclusively in the E geometry. The double bonds in 8a-c need to be reduced to obtain the saturated alkyl linker of the target molecules.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of BODIPY-α-Tocopherol: A Fluorescent Form of Vitamin E

2010

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Fluorescent nitrobenzoxadiazole analogues of α-tocopherol (NBD-α-Tocs; λ ex = 468 nm, λ em = 527 nm) have been made previously to aid study of the intracellular location and transfer of vitamin E. However, these analogues are susceptible to photobleaching while under illumination for confocal microscopy as well as in in vitro FRET transfer assays. Here we report the synthesis of three fluorescent analogues of α-tocopherol incorporating the more robust dipyrrometheneboron difluoride (BODIPY) fluorophore. A BODIPY-linked chromanol should have no intervening polar functional groups that might interfere with binding to the hydrophobic binding site of the tocopherol transfer protein (α-TTP). A key step in bringing the two ring systems together was a metathesis reaction of vinyl chromanol and an alkenyl BODIPY. An o-tolyl containing second generation Grubbs catalyst was identified as the best catalyst for effecting the metathesis without detectable alkene isomerization which, when it occurred produced a mixture of chain lengths in the alkyl linker. C8-BODIPY-α-Toc 10c (λ ex = 507 nm, λ em = 511 nm, ε 507 = 83,000 M -1 cm -1 ) having an eight-carbon chain between the chromanol and fluorophore, had the highest affinity for α-TTP (K d = 94 ± 3 nM) and bound specifically as it could not be displaced with cholesterol.

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“…An alkene-alkene scrambling cross-metathesis was used to prepare labeled sphingolipids (Eq. (226)) [1250]. A CM of an propenyl group to give an ethenyl group was used in synthesis of tuberostemonines (Eq.…”

Section: Metathesis Reactionsmentioning

confidence: 99%

Transition metals in organic synthesis: Highlights for the year 2005

Söderberg

2008

Coordination Chemistry Reviews

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One-step labelling of sphingolipids via a scrambling cross-metathesis reaction

Abstract: The alkyl chain in the backbone of sphingosine derivatives can be exchanged with functionalised (labelled) side chains in a single step under cross-metathesis reaction conditions.

Cited by 29 publications

References 14 publications

Synthesis and Immobilization of erythro‐C14‐ω‐Aminosphingosine‐1‐phosphate as a Potential Tool for Affinity Chromatography

Synthesis and Immobilization of erythro‐C14‐ω‐Aminosphingosine‐1‐phosphate as a Potential Tool for Affinity Chromatography

Synthesis and Characterization of BODIPY-α-Tocopherol: A Fluorescent Form of Vitamin E

Transition metals in organic synthesis: Highlights for the year 2005

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