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Total Synthesis of Woodrosin I—Part 1: Preparation of the Building Blocks and Evaluation of the Glycosylation Strategy

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

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

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

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Wirtz,  Cornelia
Service Department Mynott (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Mynott,  Richard
Service Department Mynott (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Zitation

Fürstner, A., Jeanjean, F., Razon, P., Wirtz, C., & Mynott, R. (2003). Total Synthesis of Woodrosin I—Part 1: Preparation of the Building Blocks and Evaluation of the Glycosylation Strategy. Chemistry – A European Journal, 9(1), 307-319. doi:10.1002/chem.200390025.


Zitierlink: http://hdl.handle.net/11858/00-001M-0000-000F-98CF-4
Zusammenfassung
The completion of the first total synthesis of the complex resin glycoside woodrosin I (1) is outlined using the building blocks described in the preceding paper. Key steps involve the TMSOTf-catalyzed coupling of diol 2 with trichloroacetimidate 3 which leads to the selective formation of orthoester 5 rather than to the expected tetrasaccharide. Diene 5, on treatment with catalytic amounts of the Grubbs carbene complex 6 or the phenylindenylidene ruthenium complex 7, undergoes a high yielding ring closing olefin metathesis reaction (RCM) to afford macrolide 8. Exposure of the latter to the rhamnosyl donor 4 in the presence of TMSOTf under “inverse glycosylation” conditions delivers compound 9 by a process involving glycosylation of the sterically hindered 2′-OH group and concomitant rearrangement of the adjacent orthoester into the desired β-glycoside. This transformation constitutes one of the most advanced applications of the Kochetkov glycosidation method reported to date. Cleavage of the chloroacetate followed by exhaustive hydrogenation completes the total synthesis of the targeted glycolipid 1.