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A New Method for the Preparation of Non-Terminal Alkynes: Application to the Total Syntheses of Tulearin A and C

MPS-Authors
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Lehr,  Konrad
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Schulthoff,  Saskia
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Ueda,  Yoshihiro
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Mariz,  Ronaldo
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Leseurre,  Lucie
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Gabor,  Barbara
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Fürstner,  Alois
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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chem_201404873_sm_miscellaneous_information.pdf
(Supplementary material), 12MB

Citation

Lehr, K., Schulthoff, S., Ueda, Y., Mariz, R., Leseurre, L., Gabor, B., et al. (2015). A New Method for the Preparation of Non-Terminal Alkynes: Application to the Total Syntheses of Tulearin A and C. Chemistry – A European Journal, 21(1), 219-227. doi:10.1002/chem.201404873.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0024-688E-7
Abstract
Lactones are known to react with the reagent generated in situ from CCl4 and PPh3 in a Wittig-type fashion to give gem-dichloro-olefin derivatives. Such compounds are now shown to undergo reductive alkylation on treatment with organolithium reagents RLi to furnish acetylene derivatives bearing the substituent R at their termini (R=Me, n-, sec-, tert-alkyl, silyl); the reaction can be catalyzed with either Cu(acac)2 or Fe(acac)3/1,2-diaminobenzene. Two alkynol derivatives prepared in this way from readily accessible lactone precursors served as the key building blocks for the total syntheses of the cytotoxic marine macrolides tulearin A (1) and C (2). The assembly of these fragile targets hinged upon ring closing alkyne metathesis (RCAM) followed by a formal trans-reduction of the resulting cycloalkynes via trans-hydrosilylation/protodesilylation.