Practical and Efficient Synthesis of a Chiral C₅ Building Block, 2-O-Allyl-d-arabinose, from Diacetone-d-glucose

 

 Buy Article Permissions and Reprints All articles of this category

Abstract

The first syntheses of a 2-O-allylpentose are described. Starting from d-arabinose (2), 2-O-allyl-d-arabinose (1) was obtained in 36-42% yield over five steps. A practical and efficient synthesis from cheap and abundant diacetone glucose yielded 56% of 1 over only three steps.

References

• 2a Cook PD. inventors; WO  9313121. As of December 2005, to the best of our knowledge, the only published reference to a 2-O-allylpentose consists of a patent (Isis Corp.):
• 2b

  For 2-O-allyl-d-ribose no preparation was described.
• 3a 3-O-Allyl-d-glucose: Hoiness DE. Wade CP. Rowland SP. Can. J. Chem.  1968,  46:  667 
  CrossrefGoogle Scholar
• 3b Ito H. Eby R. Kramer S. Schuerch C. Carbohydr. Res.  1980,  86:  193 
  CrossrefGoogle Scholar
• 3c Takeo K. Nakaji T. Shinmitsu K. Carbohydr. Res.  1984,  133:  275 
  CrossrefGoogle Scholar
• 3d Liu CM. Warren CD. Jeanloz RW. Carbohydr. Res.  1985,  136:  273 
  CrossrefGoogle Scholar
• 3e Bhattacharjya A. Chattopadhyay P. McPhail AT. McPhail DR. J. Chem. Soc., Chem. Commun.  1990,  1508 
  CrossrefGoogle Scholar
• 4a 3-O-Allyl-d-allose and 3-O-allyl-d-altrose: Shing TKM. Zhong Y.-L. Mak TCW. Wang R.-J. Xue F. J. Org. Chem.  1998,  63:  414 
  CrossrefGoogle Scholar
• 4b Shing TKM. Zhong Y.-L. Tetrahedron  2001,  57:  1573 
  CrossrefGoogle Scholar
• 5 3-O-Allyl-d-galactose: Srivastava G. Hindsgaul O. J. Carbohydr. Chem.  1991,  10:  927 
  CrossrefGoogle Scholar
• 6 Masanao M, and Ogawa T. inventors; JP 56036497,  . 3-O-Allyl-d-mannose:
• 7 For cytotoxic and antimicrobial activity of 3-O-alkyl-d-glucoses, 3-O-alkenyl-d-glucoses, and 3-O-alkenyl-d-alloses, see: Ikekawa T. Irinoda K. Saze K. Katori T. Matsuda H. Ohkawa M. Kosik M. Chem. Pharm. Bull.  1987,  35:  2894 
  CrossrefGoogle Scholar
• 9a There is evidence that d-glucose and d-galactose are oxidized by sodium periodate predominantly in the pyranose form: Hough L. Taylor TJ. Thomas GHS. Woods BM. J. Chem. Soc.  1958,  1212 
  Google Scholar
• 9b There is very little published about the behavior of 3-O-alkylhexoses and 3-O-alkenylhexoses under these conditions. Barker and Smith claimed that the oxidation of 3-O-methylglucose with sodium periodate led to 4-O-formyl-2-O-methylarabinose, but without structural proof: Barker GR. Smith DCC. Chem. Ind.  1952,  1035 
  Google Scholar
• 9c On the other hand, Qadir and Webber had reported on the instability of an allyl ether protective group in a sodium periodate-mediated oxidation of a cyclic sulfide: Qadir MH. Webber JM. J. Chem. Soc. Pak.  1986,  8:  19 
  Google Scholar
• Under the reaction conditions [Pb(OAc)₄, glacial AcOH] of the Perlin-Brice synthesis of d-erythrose from d-glucose the initial reaction product has been reported as 3,4-di-O-formyl-d-erythrose:
• 10a Perlin AS. Brice C. Can. J. Chem.  1956,  34:  541 
  Google Scholar
• 10b Perlin AS. Meth. Carbohydr. Chem.  1962,  1:  64 
  Google Scholar
• 10c

  To the best of our knowledge, there are no literature reports on the hydrolytic stability of formate esters in allyl ether protected hexoses or pentoses.

  Google Scholar
• 13 Storz T. Vasella A. Helv. Chim. Acta  1998,  81:  1896 
  CrossrefGoogle Scholar
• 14 Takeo K. Nakagen M. Teramoto Y. Carbhohydr. Res.  1990,  201:  261 
  Google Scholar
• 15 Smith AB. Rivero RA. Hale KJ. Vacaro HA. J. Am. Chem. Soc.  1991,  113:  2092 
  Google Scholar
• 16 Bols M. In Carbohydrate Building Blocks   1st ed.:  Wiley & Sons; New York: 1996.  p.11 
  Google Scholar

Current address: Thomas Storz, Amgen Inc., Chemical Process R&D, P. O. Box, One Amgen Center Drive, Thousand Oaks, CA 91320-1799, USA.

On a relative scale, d-arabinose is ca. 60-70 times more expensive than d-glucose. [16]

In our hands, recrystallization from EtOH-EtOAc (7:6, 260 mL/60 g crude 3) proved superior to the EtOH-hexane recrystallization reported previously for this compound (Takeo et al. [3c] ).

SciFinder/Beilstein searches, 12/2005. Strangely, upon contact of 1 with the skin of the fingers, an apparent muscular tickling/twitching effect lasts several minutes (anecdotal observation by T. S.).