119897-84-6

Upstream product

• 51146-39-5 trimethylsilyl ester of aci-nitrophenylmethane 
• 94594-91-9 acrylcamphorsultam 
• 932-90-1 Benzaldoxime 
• 94594-90-8 (2R)-bornane-10,2-sultam 
• 51146-39-5 trimethylsilyl phenylmethane nitronate 
• 100-39-0 benzyl bromide 
• 622-42-4 1-nitro-1-phenylmethane 
• 698-16-8 benzohydroximoyl chloride 
• 133706-01-1 ((1S,5R,7R)-10,10-Dimethyl-3,3-dioxo-3λ⁶-thia-4-aza-tricyclo[5.2.1.0^1,5]dec-4-yl)-(3-phenyl-2-trimethylsilanyloxy-isoxazolidin-5-yl)-methanone 
• 119897-86-8 N-<(4,5-dihydro-3-ethyl-(5R)-5-isoxazolyl)carbonyl>-(2R)-bornane-10,2-sultam 
• 119897-85-7 N-<(4,5-dihydro-3-methyl-(5R)-5-isoxazolyl)carbonyl>-(2R)-bornane-10,2-sultam 

Downstream Products

• 119897-89-1 (R)-3-phenyl-Δ²-isoxazoline-5-methanol 
• 94594-90-8 (2R)-bornane-10,2-sultam 

Relevant academic research and scientific papers

Diastereoselective 1,3-dipolar cycloadditions of both electronically modified phenyl-nitrile oxides and stilbenes

Menthyl carboxyloyl nitrile oxide addition is less selective for (E)-stilbene (12% d.e.) than for its corresponding (1R)-8-phenyl-menthyl (38% d.e.) or (2R)-bornane[10,2]sultam (48% d.e.) analogues. This lower selectivity is also observed when the chiral auxiliary is placed on the dipolarophile, as demonstrated by the [3 + 2] cycloadditions of p-NO2-phenyl nitrile oxide to acryloyl derivatives of (1R)-menthol (4% d.e.) and (2R)-bornane[10,2] sultam (60% d.e.). We managed to increase these diastereoselectivities by taking advantage of the Tolbert and Ali co-operative influence of two prosthetic groups, as seen in phenyl nitrile oxide addition to the bis-fumaroyl derivatives of (1R)-menthol (30% d.e.) and (2R)-bornane[10,2]sultam (98% d.e.). In the specific case of the N-acryloyl bornane[10,2]sultam, we found evidence for a small predictable negative influence of electronically deficient para-substituted phenyl nitrile oxides on diastereoselectivity (p-Me 2N, 72% d.e.; p-F, 65% d.e.; p-NO2, 60% d.e.). This may be explained by the participation of the more reactive but thermodynamically less stable syn-s-cis conformer in the reaction pathway, given its smaller difference of calculated energies in the corresponding transition states. Such an explanation is further supported by the negative influence of either a polar solvent, stabilizing these more polar transition states (phenyl nitrile oxide in hexane, 76% d.e.; CH2Cl2, 71% d.e.; MeCN, 67% d.e.), or a chelating Lewis acid (MgCl2, 66% d.e.).

Asymmetric silyl nitronate cycloadditions with bornane-10,2-sultam derivatives

Asymmetric silyl nitronate cycloadditions with N-acryloyl (2R)-bornane-10,2-sultam, N-acryloyl (2S)-bornane-10,2-sultam, and N-methacryloyl (2R)-bornane-10,2-sultam have been studied. The asymmetric silyl nitronate cycloaddition/elimination methodology pr

Asymmetric induction in silyl nitronate cycloadditions to Oppolzer's chiral sultam derivatives

Silyl nitronate cycloadditions to Oppolzer's chiral sultam derivatives, followed by the elimination of the silyl alcohols from the resulting N-silyloxyisoxazolidines, provide Δ2-isoxazolines in good stereoselectivity (ca. 89/11). The favored transition state is suggested in the light of the X-ray crystal structure of a major cycloadduct.

The Preparation of Optically Active Δ2-Isoxazolines. A Model for Asymmetric Induction in the Non Lewis Acid Catalyzed Reactions of Oppolzer's Chiral Sultam

Good diastereoselectivity (ca. 90/10) is reported in the cycloaddition reactions of Oppolzer's chiral sultam with nitrile oxides.A model is proposed which may apply to other non Lewis acid promoted reactions of this sultam.