Dienophilic reactivity of 2-phosphaindolizines: a conceptual DFT investigation

• Nosheen Beig,
• Aarti Peswani and
• Raj Kumar Bansal

Beilstein J. Org. Chem. 2022, 18, 1217–1224, doi:10.3762/bjoc.18.127

• reactivities observed experimentally. Furthermore, energies and symmetries of the lowest unoccupied molecular orbitals (LUMO) of 2-phosphaindolizines were found to be in conformity with their dienophilic reactivities. Keywords: dienophilic reactivity; electronic chemical potential; electrophilicity index

• . Furthermore, the electrophilicity index of compound 6D (0.148) is close to that of 6Cb (0.156) and like 6Cb, it is expected to undergo a DA reaction with 1,3-butadiene without the aid of a catalyst, a fact in conformity with the experimental results. Concept of local hardness/softness Fukui function analysis

Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purple

• Alexander S. Filatov,
• Olesya V. Khoroshilova,
• Anna G. Larina,
• Vitali M. Boitsov and
• Alexander V. Stepakov

Beilstein J. Org. Chem. 2022, 18, 769–780, doi:10.3762/bjoc.18.77

• ] and Domingo [48], we calculated global electrophilicity indexes (GEI, ω) for both PRP (1) and cyclopropenes 2 to determine which type of electron demand takes place during cycloaddition reactions. The global value of the electrophilicity index for azomethine ylide 1 (1.29 eV) revealed that this

• electrophilicity index (ω, eV) for PRP (1) and cyclopropenes 2.a,b,c. Supporting Information Supporting Information File 156: Experimental details for the synthesis and characterization of all compounds, copies of 1H NMR and 13C NMR spectra, X-ray data and details of calculations. Acknowledgements This research

Metal-free hydroarylation of the side chain carbon–carbon double bond of 5-(2-arylethenyl)-3-aryl-1,2,4-oxadiazoles in triflic acid

• Anna S. Zalivatskaya,
• Dmitry S. Ryabukhin,
• Marina V. Tarasenko,
• Alexander Yu. Ivanov,
• Irina A. Boyarskaya,
• Elena V. Grinenko,
• Ludmila V. Osetrova,
• Eugeniy R. Kofanov and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2017, 13, 883–894, doi:10.3762/bjoc.13.89

• -diprotonated form D. The calculated electronic characteristics of species A–F revealed that the dication D has the highest electrophilicity index ω (7.48 eV) among the other cationic species, even including trication F (Table 1). Therefore, dication D is expected to be an extremely reactive electrophile

Superelectrophilic activation of 5-hydroxymethylfurfural and 2,5-diformylfuran: organic synthesis based on biomass-derived products

• Dmitry S. Ryabukhin,
• Dmitry N. Zakusilo,
• Mikhail O. Kompanets,
• Anton A.Tarakanov,
• Irina A. Boyarskaya,
• Tatiana O. Artamonova,
• Mikhail A. Khohodorkovskiy,
• Iosyp O. Opeida and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2016, 12, 2125–2135, doi:10.3762/bjoc.12.202

• (Scheme 1). All species A, B, C, and D may play a role as reactive intermediates derived from 1a and 2 in superacids. To estimate the electrophilic properties of cations A, B, C, and D we performed quantum chemical calculations by the DFT method (Table 1). HOMO and LUMO energies, global electrophilicity

• index ω [48][49], charge distribution, and contribution of atomic orbitals into the LUMO were calculated. The dications B and D having high ω values of 9.6 and 8 eV, respectively, should be very reactive electrophiles. The carbon atom of the protonated aldehyde group in species A, B, C, and D bears a

Anthracene appended pyridinium amide–urea conjugate in selective fluorometric sensing of L-N-acetylvaline salt

• Kumaresh Ghosh,
• Tanmay Sarkar and
• Asoke P. Chattopadhyay

Beilstein J. Org. Chem. 2010, 6, 1211–1218, doi:10.3762/bjoc.6.139

• example, Figure 9 demonstrates the hydrogen-bonded complex of 1A with N-acetyl-L-valine carboxylate, where both the urea and pyridinium motifs are cooperatively involved in bonding. However, interaction between the electrophile and the nucleophile can be quantified in terms of the electrophilicity index