119897-84-6

Upstream product

• 622-42-4 1-nitro-1-phenylmethane 
• 100-39-0 benzyl bromide 
• 94594-90-8 (2R)-bornane-10,2-sultam 
• 94594-91-9 acrylcamphorsultam 
• 932-90-1 Benzaldoxime 
• 51146-39-5 trimethylsilyl ester of aci-nitrophenylmethane 
• 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 
• 51146-39-5 trimethylsilyl phenylmethane nitronate 
• 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 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.

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

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.