Iterative strategies for the synthesis of deoxypropionates

Horst, Bjorn ter; Feringa, Ben L.; Minnaard, Adriaan J.

doi:10.1039/b926265b

Cited by 94 publications

(46 citation statements)

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“…In addition to the aforementioned work by Myers, Minnaard, and Breit, the modular nature of polydeoxypropionates has also inspired the development of several other iterative synthesis strategies. 82–83 …”

Section: Many Customized Iterative Synthesis Methods Have Already Beementioning

confidence: 99%

Towards the generalized iterative synthesis of small molecules

2018

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Small molecules have extensive untapped potential to benefit society, but access to this potential is too often restricted by limitations inherent to the customized approach currently used to synthesize this class of chemical matter. In contrast, the “building block approach”, i.e., generalized iterative assembly of interchangeable parts, has now proven to be a highly efficient and flexible way to construct things ranging all the way from skyscrapers to macromolecules to artificial intelligence algorithms. The structural redundancy found in many small molecules suggests that they possess a similar capacity for generalized building block-based construction. It is also encouraging that many customized iterative synthesis methods have been developed that improve access to specific classes of small molecules. There has also been substantial recent progress toward the iterative assembly of many different types of small molecules, including complex natural products, pharmaceuticals, biological probes, and materials, using common building blocks and coupling chemistry. Collectively, these advances suggest that a generalized building block approach for small molecule synthesis may be within reach.

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Section: Many Customized Iterative Synthesis Methods Have Already Beementioning

confidence: 99%

Towards the generalized iterative synthesis of small molecules

2018

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“…Aw ide range of fascinating biological activities and pharmacological properties are associated with these structures,f or example, neutral sphingomyelinase inhibitor (+ +)-scyphostatin, [2] potent squalene synthase inhibitor zaragozic acid A, [3] antibiotics TMC-151A, [4] pheromones (+ +)-4,6,8,10,16,18-hexamethyldocosane [5] and (À)-lardolure, [6] glycolipidso fM ycobacterium tuberculosis, [7] as well as apoptosis inducer (À)-rasfonin. [9] The most common methods used to date are chiral auxiliary-controlled (aza)-enolate alkylations and conjugate additions, as well as substratecontrolled conjugate additions and allylic alkylations. [9] The most common methods used to date are chiral auxiliary-controlled (aza)-enolate alkylations and conjugate additions, as well as substratecontrolled conjugate additions and allylic alkylations.…”

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confidence: 99%

One‐Step Homologation for the Catalytic Asymmetric Synthesis of Deoxypropionates

Komiyama

et al. 2016

Chemistry A European J

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A one-step homologation protocol for the synthesis of natural products containing deoxypropionate motif is described by the combination of Zr-catalyzed asymmetric carboalumination of alkenes (ZACA)-Pd-catalyzed vinylation and ZACA-oxidation reaction. In contrast to most other synthetic strategies used to date that typically require three steps per deoxypropionate unit due to the functional-group interconversions, our one-step homologation strategy promises to provide a general and more efficient synthetic route toward deoxypropionate natural products as exemplified by significant improvements in the syntheses of intermediates and/or final products of mycolipenic acid 1 and its analogue 2, (-)-rasfonin, and syn- and anti-dicarboxylic acids 5 and 6.

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“…2), among other polyketides. [27][28][29][30] Taking advantage of this knowledge, the synthesis of 4 has been attempted with the nal goal of generating a synthetic sample of 1. To elucidate the stereochemistry of the C17 stereocenter of 4, an initial synthetic route has been devised.…”

Section: 25mentioning

confidence: 99%

Total synthesis, stereochemical elucidation and biological evaluation of Ac₂SGL; a 1,3-methyl branched sulfoglycolipid from Mycobacterium tuberculosis

et al. 2013

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Total synthesis, stereochemical elucidation and biological evaluation of Ac(2)SGL; a 1,3-methyl branched sulfoglycolipid from Mycobacterium tuberculosis Geerdink, Danny; ter Horst, Bjorn; Lepore, Marco; Mori, Lucia; Puzo, Germain; Hirsch, Anna; Gilleron, Martine; de Libero, Gennaro; Minnaard, Adriaan IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 2012Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Geerdink, D., ter Horst, B., Lepore, M., Mori, L., Puzo, G., Hirsch, A. K. H., ... Minnaard, A. J. (2012). Total synthesis, stereochemical elucidation and biological evaluation of Ac(2)SGL; a 1,3-methyl branched sulfoglycolipid from Mycobacterium tuberculosis. Chemical Science, 4(2), 709-716. DOI: 10.1039/c2sc21620e Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Mycobacterium tuberculosis, the causative agent of tuberculosis (TB), continues to represent a challenging pathogen causing many deaths. A reason for the persistence of this pathogen is the cell-envelope composition, which consists of long-tailed (glyco)lipids, involved in the modulation of the host immune response. Diacylated sulfoglycolipid Ac 2 SGL (1), found in the cell envelope, is a potent antigen that stimulates the immune response towards TB. This observation suggests the application of 1 as part of a vaccine. Here, we report the first asymmetric total synthesis of 1. Two approaches were developed for the synthesis of hydroxyphthioceranic acid (4), its polypropionate part, thereby establishing the absolute stereochemistry of the C17 hydroxyl function to be of (R)-configuration. Subsequently, 4 was regioselectively connected to the trehalose core and after selective sulfation and a final fourfold deprotection step, pure 1 was obtained. The identity of synthetic and natural 1 was confirmed by NMR and mass analysis, Furthermore, synthetic 1 shows identical biological function to 1 and activates CD1b-restricted and Ac 2 SGL-specific T cells that are highly sensitive to minimal structural modifications of 1 with the same potency. A modeling study is presented to point out the structural features of 1 that are important for binding to the antigen-presenting molecule CD1b and to the T-cell receptor. IntroductionTuber...

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Iterative strategies for the synthesis of deoxypropionates

Cited by 94 publications

References 89 publications

Towards the generalized iterative synthesis of small molecules

Towards the generalized iterative synthesis of small molecules

One‐Step Homologation for the Catalytic Asymmetric Synthesis of Deoxypropionates

Total synthesis, stereochemical elucidation and biological evaluation of Ac₂SGL; a 1,3-methyl branched sulfoglycolipid from Mycobacterium tuberculosis

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Iterative strategies for the synthesis of deoxypropionates

Cited by 94 publications

References 89 publications

Towards the generalized iterative synthesis of small molecules

Towards the generalized iterative synthesis of small molecules

One‐Step Homologation for the Catalytic Asymmetric Synthesis of Deoxypropionates

Total synthesis, stereochemical elucidation and biological evaluation of Ac2SGL; a 1,3-methyl branched sulfoglycolipid from Mycobacterium tuberculosis

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Total synthesis, stereochemical elucidation and biological evaluation of Ac₂SGL; a 1,3-methyl branched sulfoglycolipid from Mycobacterium tuberculosis