14525-88-3

Upstream product

• 2039-82-9 1-bromo-4-ethenyl-benzene 
• 1200806-90-1 1-(octane-1-sulfonyl)-4-phenyl-1H-1,2,3-triazole 
• 100-42-5 styrene 
• 536-74-3 phenylacetylene 
• 766-96-1 4-bromo-1-ethynylbenzene 
• 73900-14-8 1-bromo-4-(diazomethyl)benzene 
• 908094-04-2 phenyldiazomethane 
• 1122-91-4 4-bromo-benzaldehyde 
• 100-52-7 benzaldehyde 
• 75-11-6 diiodomethane 
• 4714-24-3 1-bromo-4-styrylbenzene 

Downstream Products

• 20822-00-8 5-(4-bromophenyl)-3-phenyl-4,5-dihydroisoxazole 
• 20822-01-9 3-(4-bromophenyl)-5-phenyl-4,5-dihydro-isoxazole 
• 53573-22-1 5-(p-bromophenyl)-3-phenyl-2-isoxazole 
• 53573-21-0 3-(4-bromophenyl)-5-phenylisoxazole 

Relevant academic research and scientific papers

Adiabatic process of higher electronically excited states: luminescence from an excited state biradical generated by irradiation of benzophenone-substituted cyclopropanes

Adiabatic photochemical reactions of cyclopropanes possessing a benzophenone moiety (trans- and cis-5), which generate a luminescent excited biradical 16??*, were studied. Various photochemical and spectroscopic techniques were used for this purpose. Excitation (350 nm, n,π* band) of 5 at 77?K affords the lowest excited state 15* that undergoes intersystem crossing to form 35*, which deactivates through phosphorescence. In contrast, 295-nm excitation (π,π* band) of 5 affords the higher electronically excited state 15**, which undergoes adiabatic C–C bond cleavage reaction to form the excited biradical 16??* that luminesces at 630?nm. The results suggest that 5 follows 2 photoreaction modes depending on the excitation wavelength, a finding that disobeys Kasha's rule.

Enantioselective Cyclobutenylation of Olefins Using N-Sulfonyl-1,2,3-Triazoles as Vicinal Dicarbene Equivalents

Cyclobutenes are highly useful synthetic intermediates as well as important motifs in bioactive small molecules. Herein, we report a regio-, chemo-, and enantioselective synthesis of cyclobutenes from olefins using N-sulfonyl-1,2,3-triazoles as vicinal dicarbene equivalents or alkyne [2 + 2] cycloaddition surrogates. Terminal and cis-olefins can be transformed into enantioenriched cyclopropanes via rhodium catalysis. Then, in one pot, treatment of these intermediates with tosyl hydrazide and base effects diazo formation followed by rhodium-catalyzed ring expansion to yield enantioenriched cyclobutenes. These cyclobutenes can be transformed into highly substituted, enantioenriched cyclobutanes, including structures relevant to natural product scaffolds.

Silylium-Ion-Promoted Ring-Opening Hydrosilylation and Disilylation of Unactivated Cyclopropanes

A silylium-ion-promoted ring-opening hydrosilylation of unactivated cyclopropanes is reported. The reaction is facilitated by the γ-silicon effect, and the regioselectivity is influenced by various stabilizing effects on the carbenium-ion intermediates, including the β-silicon effect. The experimental observations are in accord with the computed reaction mechanism. The work also showcases the ability of silylium ions to isomerize cyclopropyl to allyl groups, and the resulting α-olefins engage in a silylium-ion-mediated disilylation with hexamethyldisilane.

Iron-catalyzed synthesis of cyclopropanes by in situ generation and decomposition of electronically diversified diazo compounds

The modular synthesis of a variety of trans 1,2-disubstituted cyclopropanes in a safe and user-friendly one-pot iron-catalyzed cyclopropanation reaction is described. Easily synthesized N-nosylhydrazones are used as diazo precursors, allowing the in situ generation of electron-rich diazo compounds under mild reaction conditions and their direct participation in the cyclopropanation reaction.

THE MATRIX EFFECT ON STEREOSELECTIVITY OF OLEFIN CYCLOPROPANATION BY ARYLCARBENE

Temperature studies of addition of phenylcarbene to styrene showed that stereoselectivity changed rather dramatically as the reaction phase changed.