α-Chloronitroso compounds derived from carbohydrate ketones: Cycloadditions with cyclic dienes, a synthesis of (-)-physoperuvine and a formal synthesis of (+)-epibatidine

Adrian Hall, Patrick D. Bailey, David C. Rees, Georgina M. Rosair, Richard H. Wightman

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

1,2-O-Isopropylidene-a-D-xylofuranose 9 was converted into 5-O-(tert-butyldiphenylsilyl)-3-chloro-3-deoxy-l,2-O-isopropylidene-3-C-nitroso- a-D-xylofuranose 17 in four steps, and a similar a-chloronitroso compound 8 was synthesised from 1,2:5,6-di-O-isopropylidene-?-D-glucofuranose 6, the structures of 8 and 17 being confirmed by X-ray crystallography. Reaction of 8 or 17 with cyclohexa-1,3-diene in the presence of small amounts of water gave the cycloadduct (1S,4R)-3-aza-2-oxabicyclo[2.2.2]oct-5-ene, as its hydrochloride (-)-2, in =96% ee. Reactions of either 8 or 17 with cyclohepta-l,3-diene similarly gave (1.R,5S)-7-aza-6-oxabicyclo[3.2.2]non-8-ene hydrochloride (-)-25 with =96% ee, but reactions with cyclopentadiene proceeded differently, with 17 giving the nitrone (E)-(3R,5R)-3-[5'-O-(tert-butyldiphenylsilyl)-3'-deoxy-1', 2'-O-isopropylidene-a-D-erythro-Pentofuranos-3'-ylideneamino]- 5-chlorocyclopentene N-oxide 19, the structure of which was determined by X-ray crystallography. The dihydrooxazines (-)-25 and (-)-2 were used in syntheses of (-)-physoperuvine (-)-34 and (+)-epibatidine (+)-40, respectively. A pseudoenantiomeric a-chloronitroso compound 51 was also prepared from 2,3-O-isopropylidene-a-L-sorbofuranose 44, and reaction of 51 with cyclohexa-1,3-diene gave (+)-2 with 97% ee. © The Royal Society of Chemistry 2000.

Original languageEnglish
Pages (from-to)329-343
Number of pages15
JournalJournal of the Chemical Society, Perkin Transactions 1
Issue number3
Publication statusPublished - 2000

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