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

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.

hemiacetals - carbohydrates - oxidation - periodate cleavage - allyl - d-arabinose

References

1

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

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 

3b Ito H. Eby R. Kramer S. Schuerch C. Carbohydr. Res.  1980,  86:  193 

3c Takeo K. Nakaji T. Shinmitsu K. Carbohydr. Res.  1984,  133:  275 

3d Liu CM. Warren CD. Jeanloz RW. Carbohydr. Res.  1985,  136:  273 

3e Bhattacharjya A. Chattopadhyay P. McPhail AT. McPhail DR. J. Chem. Soc., Chem. Commun.  1990,  1508 

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 

4b Shing TKM. Zhong Y.-L. Tetrahedron  2001,  57:  1573 

5 3-O-Allyl-d-galactose: Srivastava G. Hindsgaul O. J. Carbohydr. Chem.  1991,  10:  927 

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 

8

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

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 

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 

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 

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 

10b Perlin AS. Meth. Carbohydr. Chem.  1962,  1:  64 

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.

11

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] ).

12

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.).

13 Storz T. Vasella A. Helv. Chim. Acta  1998,  81:  1896 

14 Takeo K. Nakagen M. Teramoto Y. Carbhohydr. Res.  1990,  201:  261 

15 Smith AB. Rivero RA. Hale KJ. Vacaro HA. J. Am. Chem. Soc.  1991,  113:  2092 

16 Bols M. In Carbohydrate Building Blocks   1st ed.:  Wiley & Sons; New York: 1996.  p.11