(Trifluoromethyl)sulfonyl (triflyl) migration. Synthesis of 6,3’-anhydro-3-benzyl-l-(5-chloro-5-deoxy-β-D-xylofuranosyl)barbituric acid from the 2’-trifluoromethanesulfonate (triflate) of 6,5’-anhydro-3-benzyl-1-β-D-ribofuranosylbarbituric acid Journal Article

  

Authors:	Pankiewicz, K. W.; Nawrot, B. C.; Watanabe, K. A.
Article Title:	(Trifluoromethyl)sulfonyl (triflyl) migration. Synthesis of 6,3’-anhydro-3-benzyl-l-(5-chloro-5-deoxy-β-D-xylofuranosyl)barbituric acid from the 2’-trifluoromethanesulfonate (triflate) of 6,5’-anhydro-3-benzyl-1-β-D-ribofuranosylbarbituric acid
Abstract:	The first evidence of (trifluoromethyl)sulfonyl (triflyl) migration is presented. The 2’,3’-0-stannylene derivative of 6,5’ acid (1) afforded a 9:1 mixture of isomeric 2’- and 3’-triflates 2 and 3 upon treatment with triflyl chloride in N,N-dimethylformamide. On acetylation, 2 and 3 afforded their corresponding acetyl derivatives 4 and 5. Compound 4 was converted into 6,2’-anhydro-3-benzyl-l-(3-O-acetyl-5-chloro-5-deoxy-β-D-arabinofuranosyl)barbituric acid (6) by treatment with LiCl in hexamethylphosphoric triamide (HMPA), whereas 5 afforded the 6,3’-anhydro-xylo isomer 7. Compounds 6 and 7 were reduced to the 5’-deoxy nucleosides 8 and 9, respectively. Treatment of both 2’- and 3’-triflates 2 and 3 with LiCl in HMPA afforded, exclusively, the same 6,3’-anhydro-xylo derivative 10, which was acetylated to 7. The triflyl group on C-2’ in 2 migrated to C-3’ prior to the formation of the 6,3’-anhydro linkage during the conversion to 10. A plausible mechanism is discussed. © 1986, American Chemical Society. All rights reserved.
Keywords:	nonhuman; drug synthesis; nuclear magnetic resonance; theoretical study; proton nuclear magnetic resonance; drug identification; drug analysis; 6,3' anhydro 3 benzyl 1 (5 chloro 5 deoxy beta d xylofuranosyl)barbituric acid; 6,5' anhydro 3 benzyl 1 beta d ribofuranosylbarbituric acid triflate
Journal Title:	Journal of Organic Chemistry
Volume:	51
Issue:	9
ISSN:	0022-3263
Publisher:	American Chemical Society
Date Published:	1986-05-01
Start Page:	1525
End Page:	1529
Language:	English
DOI:	10.1021/jo00359a027
PROVIDER:	scopus
DOI/URL:	https://www.scopus.com/inward/record.uri?eid=2-s2.0-0022544891&doi=10.1021%2fjo00359a027&partnerID=40&md5=93b193a96246439cdb0292f4861d263c
Notes:	Article -- Export Date: 18 August 2021 -- Source: Scopus

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