Ferrocenoyl-adenines: substituent effects on regioselective acylation

• Mateja Toma,
• Gabrijel Zubčić,
• Jasmina Lapić,
• Senka Djaković,
• Davor Šakić and
• Valerije Vrček

Beilstein J. Org. Chem. 2022, 18, 1270–1277, doi:10.3762/bjoc.18.133

• quantitative comparison between different sites, the condensed Fukui function based on atomic charges was calculated. We calculated total populations for all nitrogen atoms in the adenine anion in its N and N−1 electron states to obtain the condensed f− descriptor according to the equation for the

• Fukui function f- (right) for the adenine anion (isovalue = 0.008) calculated with NPA charges. Dependence of N9-isomer product ratio (%), in the reaction between FcCOCl and adenine anions 1–6, on the averaged perpendicular Sterimol parameter B = (B1 + B5)/2 of the C6-substituent (open circles; in the

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

• ; Fukui function; global hardness; nucleophilicity index; 2-phosphaindolizines; Introduction In 1988, we developed a simple synthetic method for the synthesis of 1,3-azaphospholo[1,5-a]pyridine derivative (1, R1 = Me, R2 = PhCO) from the reaction of 2-ethyl-1-phenacylpyridinium bromide with PCl3 and Et3N

• reagents [19]. Thus a quantitative descriptor, the Fukui function was defined as for nucleophilic attack and for electrophilic attack, where ρN+1(r), ρN(r), and ρN−1(r) are the electron densities at a point r in the system with N+1, N, and N−1 electrons, respectively, all with the ground-state geometry

• of the N-electron system. It was concluded that the regions of a molecule with a large Fukui function are chemically softer than the regions where the Fukui function is small. Thus, by invoking the HSAB principle it becomes possible to predict the behavior of a particular site in the molecule towards

Thiophene/selenophene-based S-shaped double helicenes: regioselective synthesis and structures

• Mengjie Wang,
• Lanping Dang,
• Wan Xu,
• Zhiying Ma,
• Liuliu Shao,
• Guangxia Wang,
• Chunli Li and
• Hua Wang

Beilstein J. Org. Chem. 2022, 18, 809–817, doi:10.3762/bjoc.18.81

• photocyclization reaction sites of 5 were predicted by the orbital-weighted Fukui function in Multiwfn using Gaussian 09 [31][32] at the B3LYP/6-31G** [33] level of theory to verify the reaction-site selectivity of oxidative photocyclization further. Results showed that the conformations of 5a are varied, but the

• orbital-weighted Fukui function is not connected to conformation. In the orbital-weighted Fukui function, the larger the isosurface distribution, the higher the activity of reactions. Thus the 4 and 6-positions of benzene are the most likely sites for reaction (see Supporting Information File 1, Figure

cis–trans Isomerization of silybins A and B

• Michaela Novotná,
• Radek Gažák,
• David Biedermann,
• Florent Di Meo,
• Petr Marhol,
• Marek Kuzma,
• Lucie Bednárová,
• Kateřina Fuksová,
• Patrick Trouillas and
• Vladimír Křen

Beilstein J. Org. Chem. 2014, 10, 1047–1063, doi:10.3762/bjoc.10.105

• with two Walden inversions). The possibility of acetyl group participation was refuted by the reaction of 2 in DMF, so that no isomerization took place at C-11. Moreover, in DMF the f(r) Fukui function is totally displaced into the E-ring (Figure 7b), so that the O-12 atom loses its nucleophilic

• few years. The Fukui function fk(r) has become one of these powerful tools, providing an atomic picture of hardness. For a given atom k, it is given by where fk+(r) and fk−(r) are the electrophilic and nucleophilic contributions of the Fukui function calculated as follows: and , where qk(N), qk(N−1

• ) and qk(N + 1) are the electronic population of atom k in its neutral, radical-cation and radical-anion forms, respectively. In this study, the Fukui function is used to partially rationalize BF3 complexation. In this case, the nucleophilic contribution is the most important parameter. It must be

The regioselective synthesis of spirooxindolo pyrrolidines and pyrrolizidines via three-component reactions of acrylamides and aroylacrylic acids with isatins and α-amino acids

• Tatyana L. Pavlovskaya,
• Fedor G. Yaremenko,
• Victoria V. Lipson,
• Svetlana V. Shishkina,
• Oleg V. Shishkin,
• Vladimir I. Musatov and
• Alexander S. Karpenko

Beilstein J. Org. Chem. 2014, 10, 117–126, doi:10.3762/bjoc.10.8

• . The most stable conformation of benzoylacrylic acid possesses the benzoyl and carboxylic groups trans to each other (Figure 5). The atom charges for the analysis of the Fukui function indices were calculated within the Natural Bonding Orbitals theory [40] with the NBO 5.0 program [41], that revealed

• crystal phase as solvate with methanol according to X-ray diffraction data. Conformations of acrylamide and benzoylacrylic acid. The Fukui function indices of acrylamide, azomethine ylide and benzoylacrylic acid. The selected COSY, NOESY and HMBC correlations of the signals in the 1H and 13C NMR spectra