Regiospecific formation of the nitromethyl-substituted 3-phenyl-4,5-dihydroisoxazole via [3 + 2] cycloaddition

Abstract

Abstract5-(Nitromethyl)-3-phenyl-4,5-dihydroisoxazole was obtained as a product of a high-yielding [3 + 2] cycloaddition reaction of in situ-generated benzonitrile N-oxide and 3-nitroprop-1-ene. For the first time, the regiochemistry of this reaction was unambiguously proven by X-ray structural analysis. The quantum-chemical calculation performed at the M06-2X/6-31G(d) (PCM) theoretical level affords a basis for explaining the course of reaction as well as the nature of transition states. Next, further DFT calculations together with spectral data shed light on structural aspects of the product.Graphical abstract Electronic supplementary materialThe online version of this article (10.1007/s00706-018-2227-6) contains supplementary material, which is available to authorized users.

The Molecular Mechanism of the Formation of Four-Membered Cyclic Nitronates and Their Retro (3 + 2) Cycloaddition: A DFT Mechanistic Study

“…A similar approach, entering in Molecular Electron Density Theory (MEDT) [ 27 ], to elucidate the molecular mechanism has been used successfully in various types of reactions. The used computational method has been shown to give results that are in complete agreement with experimental outcomes of previous reactions [ 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 ].…”

Competition between [2 + 1]- and [4 + 1]-cycloaddition mechanisms in reactions of conjugated nitroalkenes with dichlorocarbene in the light of a DFT computational study

“…The most universal methodology for preparing nitrofunctionalized cyclic compounds is cycloaddition reactions involving respective conjugated nitroalkenes (CNA) [4,11]. In this way, several four- [12,13], five - [14][15][16][17], and six-membered [18][19][20][21] nitro-cycles have been prepared. This is possible via [2 + 2], [3 + 2], and [4 + 2] cycloadditions, respectively.…”

New Rigid Polycyclic Bis(phosphane) for Asymmetric Catalysis

“…The quantum chemical calculation performed at the M062x/LANL2DZ theoretical level [27,28], which is specially dedicated to precise energetic considerations and has recently been applied in the simulation of energetic and structural analyses of molecules with similar structural moieties [29,30,31,32,33], allows us to compare the geometry of the molecules of phosphines 6 , their dioxides and complexes that were not crystallised in crystals, well-measurable by a single crystal X-ray diffraction. The geometry optimisation for the structure [Pd( 6q )Cl 2 ] was therefore performed and the obtained geometry parameters of [Pd( 6q )Cl 2 ] calc were compared with those received from the X-ray diffraction experiments for [Pd( 6q )Cl 2 ] xray .…”