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

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

References

• 1a Corey EJ. Seebach D. Angew. Chem., Int. Ed. Engl.  1965,  4:  1075 ; Angew. Chem., 1965, 77, 1134
• 1b Seebach D. Jones NR. Corey EJ. J. Org. Chem.  1968,  33:  300 
• 1c Yus M. Nájera C. Foubelo F. Tetrahedron  2003,  59:  6147 
• 2a El-Ashmawy AE. Horton D. Carbohydr. Res.  1965,  1:  164 
• 2b El-Ashmawy AE. Horton D. Magbanua LG. Tronchet JMJ. Carbohydr. Res.  1968,  6:  299 
• 2c Benzing L. Perry MB. Can. J. Chem.  1978,  56:  691 
• 2d Paul B. Korytnyk W. Carbohydr. Res.  1979,  72:  247 
• 2e Hanessian S. Sahoo SP. Can. J. Chem.  1984,  62:  1400 
• 2f Rollin P. Tetrahedron Lett.  1987,  28:  3813 
• 2g Anaya J. Fernandez-Mateos A. Grande M. Martianez J. Ruano G. Rubio-Gonzalez M. Tetrahedron  2003,  59:  241 
• 2h Ruano G. Martianez J. Grande M. Anaya J. J. Org. Chem.  2003,  68:  2024 
• 3a Angibeaud P. Bosso C. Defaye J. Horton D. J. Chem. Soc., Perkin Trans. 1  1979,  1583 
• 3b Barton DHR. Gateau-Olesker A. Anaya-Mateos J. Cléophax J. Géro SD. Chiaroni A. Riche C. J. Chem. Soc., Perkin Trans. 1  1990,  3211 
• 3c

  Chen, Y.-L.; Leguijt, R.; Redlich, H. J. Carbohydr. Chem. 2006, in press.

• 4 With the exception of a recent publication from this group using dilithiated N-acetyl-d-glucosamine trimethylene dithioacetal derivatives for cyclization reactions, see: Chen Y.-L. Leguijt R. Redlich H. Synthesis  2006,  2242 
• 5 Anaya-Mateos J. Barton DHR. Géro SD. Grande M. Hernando JIM. Laso NM. Tetrahedron: Asymmetry  1995,  6:  609 
• 6a Paulsen H. Roden K. Sinnwell V. Koebernick W. Angew. Chem., Int. Ed. Engl.  1976,  15:  439 
• 6b Paulsen H. Roden K. Sinnwell V. Luger P. Liebigs Ann. Chem.  1981,  2009 
• 7a Grierson DS. Harris M. Husson H.-P. J. Am. Chem. Soc.  1980,  102:  1064 
• 7b Diez A. Castells J. Forns P. Rubiralta M. Grierson DS. Husson H.-P. Solan X. Font-Bardia M. Tetrahedron  1994,  50:  6585 
• 8 Seebach D. Maestro MA. Sefkow M. Neidlein A. Sternfeld F. Adam G. Sommerfeld T. Helv. Chim. Acta  1991,  74:  2112 

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) ų, ρ_calc = 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 (R_int = 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: [phone], E-mail: [e-mail]].