A facile synthesis of 4,6-O-benzylidene glucal

Tetrahedron Asymmetry

Volumn 14, Issue 13, 2003, Pages 1767-1769

  Chambers, David J ^a   Evans, Graham R ^b   Fairbanks, Antony J ^a  

^a UNIVERSITY OF OXFORD   (United Kingdom)

^b UCB PHARMA   (Belgium)

Author keywords

[No Author keywords available]

Indexed keywords

4,6 BENZYLIDENEGLUCOSE; ALPHA METHYLGLUCOSIDE; IODIDE;

ARTICLE; CHEMICAL REACTION; PRIORITY JOURNAL; SYNTHESIS;

EID: 0038094509     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(03)00288-X     Document Type: Article

References (32)

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21. 4), filtered, concentrated in vacuo, and purified by flash column chromatography (petrol:ethyl acetate, 4:1) to give the desired mono-triflate 5 and di-triflate 6 as a 20:1 mixture (combined yield of 85%), which could be recrystallised from ether/petrol to give the pure mono-triflate 5 (1.677 g, 77%) as a white crystalline solid.
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27. 4), filtered, concentrated in vacuo, and the residue purified by flash column chromatography (petrol:ethyl acetate, 4:1) to afford iodide 7 (2.00 g, 83%) as a white crystalline solid.
28. No reaction occurred in ether, acetone, or DMF below 80°C. Although displacement did occur in DMF above 80°C, reductive elimination of the product was observed producing iodine, which in turn cleaved the 4,6-O-benzylidene protecting group. Addition of co-reductants was not able to suppress this benzylidene cleavage.
29. 3), 64.1 (d), 66.0 (d, C-3), 68.6 (t, C-6), 81.3 (d), 102.2 (d, PhC̄H), 103.7(d, C-1), 126.3, 128.4, 129.3 (3×d, Ar-C̄H), 137.0 (s, Ar-C̄).
30. Alternative reduction conditions were also attempted; transmetallation with MeLi or the use of Zn in EtOH gave only low yields of product and in the latter case a major side product was identified as the 2-deoxy methyl glycoside. Notably no cleavage of the 4,6-O-benzylidene was observed in the acetic acid/dichloromethane solvent system.
31. 4), filtered, concentrated in vacuo and purified by flash column chromatography (petrol:ethyl acetate, 3:1) to give glucal 1 (1.11 g, 69%) as a white crystalline solid.
32. 6,6′ 10.4 Hz, H-6′), 4.49-4.52 (1H, m, H-3), 4.77 (1H, dd, J 2.0 Hz, 6.4 Hz, H-2), 5.60 (1H, s, PhCH), 6.33-6.35 (1H, m, H-1), 7.36-7.54 (5H, m, 5×Ar-H).