96093-85-5

Upstream product

• 95517-29-6 1-C-nitroso-2,3:5,6-di-O-isopropylidenemannofurasonyl chloride 
• 1165952-91-9 cyclohexa-1,3-diene 
• 217438-75-0 1,6-Bis-O-(tert-butyldimethylsilyl)-4-chloro-4-deoxy-2,3-O-isopropylidene-4-C-nitroso-α-L-sorbofuranose 

Downstream Products

• 121129-39-3 (1R,4S)-3-<(2R)-2-hydroxy-2-phenylacetyl>-2-oxa-3-azabicyclo<2.2.2>oct-5-ene 
• 140224-36-8 (1R,4S)-3-<(2R)-2-methoxy-2-phenylacetyl>-2-oxa-3-azabicyclo<2.2.2>oct-5-ene 
• 503817-66-1 (1R,4S)-3-benzyloxycarbonyl-3-aza-2-oxabicyclo[2.2.2]oct-5-ene 
• 133378-87-7 (2R,4aS,5aS,8R,9aR,9bR)-Perhydro-5-<(1R,4S)-2-oxa-3-azabicyclo<2.2.2>oct-5-ene-3-carbonyl>-2,8-diphenyl-2H,5H,8H-bis<1.3>dioxino<5,4-b:4',5'-d>pyrrole 
• 96093-88-8 N-((1S,4R)-4-Hydroxy-cyclohex-2-enyl)-benzamide 
• 140160-64-1 (1R,4S)-3-<(phenyloxy)carbonyl>-2-oxa-3-azabicyclo<2.2.2>oct-5-ene 
• 503817-74-1 (1R,2S,3R,4S)-2,3-O-isopropylidenedioxy-4-benzyloxycarbonylaminocyclohexanol 
• 503817-72-9 (1R,4S,5R,6R)-5,6-O-isopropylidenedioxy-3-benzyloxycarbonyl-3-aza-2-oxabicyclo[2.2.2]octane 
• 503817-75-2 (2R,3R,4S)-2,3-O-isopropylidenedioxy-4-(benzyloxycarbonylamino)cyclohexanone 
• 503817-70-7 (1R,4S,5R,6R)-5,6-dihydroxy-3-benzyloxycarbonyl-3-aza-2-oxabicyclo[2.2.2]octane 
• 503817-68-3 (4S)-benzyloxycarbonylamino-2-cyclohexenone 
• 503817-67-2 (4S)-benzyloxycarbonylamino-2-cyclohexenol 

Relevant academic research and scientific papers

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

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.

Diastereoselective Diels-Alder Reactions with α-Chloronitroso Saccharides

The α-chloronitroso reagent 2 obtained from ribose via the lactone oxime 3 reacts with the dienes 6-10 at low temperature to give the chiral dihydrooxazines 11-16 in 63-96percent yield and >/=96percent enantiomeric excess.The reagents 1 and 2 which are ap