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Synthesis 2006(24): 4212-4218  
DOI: 10.1055/s-2006-950359
PAPER
© Georg Thieme Verlag Stuttgart · New York

Trimethylene Dithioacetals of Carbohydrates, Part 6: C-C Coupling Reactions­ of Dilithiated N-Acetyl-d-glucosamine Trimethylene Dithioacetal Derivatives

Yue-Lei Chena,b, Robin Leguijta, Hartmut Redlich*a, Roland Fröhlicha
a Organisch-Chemisches Institut der Westfälischen Wilhelms-Universität Münster, Corrensstraße 40, 48149 Münster, Germany
Fax: +49(251)839772;
b NRW Graduate School of Chemistry, Corrensstraße 36, 48149 Münster, Germany
e-Mail: redlich@uni-muenster.de;
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Publication History

Received 30 April 2006
Publication Date:
02 November 2006 (online)

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Abstract

While 3,4;5,6-di-O-isopropylidene-N-phthaloyl-d-glucosamine propane-1,3-diyl dithioacetal (2) underwent fast β-elimination, the corresponding N-acetyl derivative 3 was easily deprotonated with butyllithium to form the dilithiated intermediate 7, which was stabilized by the α-lithium imidate and reacted well with various electrophilic reagents to yield the chain-elongated products 11a-c and 12a,b. The reaction between the intermediate 7 and an unreactive 3-ulose 13 indicates that the former has pronounced reactivity compared to its α-oxy analogue. The N-tert-butoxy­carbonyl derivative 4 also reacted with electrophilic reagents to yield the C-C coupling products, but always with lower yields.

Key words

d-glucosamine trimethylene dithioacetal - chiral pool - carbanion - imidate anion - chain extension

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1x

For X-ray analysis.

9

X-ray crystal structure analysis for compound 14: formula C29H47NO11S2·C3H6O, M = 707.87, colorless crystal 0.35 0.35 0.30 mm, a = 13.879(1), c = 33.656(1) Å, γ = 120°,
V = 5614.5(6) Å3, ρcalc = 1.256 g cm-3, µ = 1.782 mm-1, empirical absorption correction (0.574 ≤ T ≤ 0.617), Z = 6, hexagonal, space group P65 (No. 170), λ = 1.54178 Å, T = 223 K, ω and φ scans, 7761 reflections collected (h, k, l), [(sinθ)/λ] = 0.59 Å-1, 4566 independent (Rint = 0.023) and 3554 observed reflections [I ÷ 2 σ (I)], 439 refined parameters, R = 0.051, wR2 = 0.132, Flack parameter 0.04(2), max. residual electron density 0.52 (-0.17) e Å-3, hydrogen atoms calculated and refined as riding atoms.
Data set was collected with a Nonius KappaCCD diffractometer. Programs used: (a) Data collection COLLECT (Nonius B.V., 1998). (b) Data reduction Denzo-SMN: Otwinowski, Z.; Minor, W. Methods Enzymol. 1997, 276, 307. (c) Absorption correction Denzo: Otwinowski, Z.; Borek, D.; Majewski, W.; Minor, W. Acta Crystallogr. A 2003, 59, 228. (d) Structure solution SHELXS-97: Sheldrick, G. M. Acta Crystallogr. A 1990, 46, 467. (e) Structure refinement SHELXL-97: Sheldrick, G. M.; Universität Göttingen, 1997. (f) Graphics SCHAKAL: Keller, E.; Universität Freiburg, 1997.
CCDC 623504 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033, E-mail: deposit@ccdc.cam.ac.uk].