145264-12-6Relevant academic research and scientific papers
Catalytic Asymmetrization of meso-3,7-Bis-siloxycycloheptene by Chiral Rhodium(I)-binap Catalyst: the Enantiocontrolled Asymmetric Synthesis of (-)-(S)-Physoperuvine
Hiroya, Kou,Ogasawara, Kunio
, p. 2205 - 2206 (1995)
Catalytic asymmetrization of meso-3,7-bis-tert-butyldimethylsiloxycycloheptene occurs in the presence of a chiral rhodium(I) binap catalyst to give optically active 4-tert-butyldimethylsiloxycycloheptanone in 70percent ee after hydrolytic workup, the (R)-enantiomer of which has been transformed into (-)-(S)-physoperuvine, the major alkaloid of Physalis peruviana.
α-Chloronitroso compounds derived from carbohydrate ketones: Cycloadditions with cyclic dienes, a synthesis of (-)-physoperuvine and a formal synthesis of (+)-epibatidine
Hall, Adrian,Bailey, Patrick D.,Rees, David C.,Rosair, Georgina M.,Wightman, Richard H.
, p. 329 - 343 (2007/10/03)
1,2-O-Isopropylidene-α-D-xylofuranose 9 was converted into 5-O-(tert-butyldiphenylsilyl)-3-chloro-3-deoxy-1,2-O-isopropylidene-3-C-nitroso- α-o-xylofuranose 17 in four steps, and a similar α-chloronitroso compound 8 was synthesised from 1,2:5,6-di-O-isopropylidene-α-o-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-1,3-diene similarly gave (1R,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)-(3 R,5 R)-3-[5′-O-(tert-butyldiphenylsilyl)-3′-deoxy-1′,2′-O-is opropylidene-α-D-erythro-pentofuranos-3′-ylidene-amino]-5-chlorocycl opentene 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 α-chloronitroso compound 51 was also prepared from 2,3-O-isopropylidene-α-L-sorbofuranose 44, and reaction of 51 with cyclohexa-1,3-diene gave (+)-2 with 97% ee.
Asymmetric cycloadditions of dienes to chloronitroso compounds derived from carbohydrate ketones: Syntheses of (-)-physoperuvine and (+)-epibatidine
Hall, Adrian,Bailey, Patrick D.,Rees, David C.,Wightman, Richard H.
, p. 2251 - 2252 (2007/10/03)
An α-chloronitroso compound derived from D-xylose undergoes cycloadditions with cyclic dienes to give bicyclic dihydrooxazines of high enantiomeric purity; such adducts were used in a synthesis of (-)-physoperuvine and a formal synthesis of (+)-epibatidin
Oxygenation of N-Cyclohepthylbenzamides with Beauveria sulfurescens
Johnson, Roy A.,Herr, Milton E.,Murray, Herbert C.,Krueger, William C.,Pschigoda, Loraine M.,Duchamp, David J.
, p. 7212 - 7216 (2007/10/02)
The oxygenation of several N-cycloheptylbenzamides by fermentation with the fungus Beauveria sulfurescens (ATCC 7159) has been studied.Structures have been determined by chemical and physical methods.Enantioselectivity was observed in the oxygenation proc
