Heterocycle-guided synthesis of m-hetarylanilines via three-component benzannulation

• Andrey R. Galeev,
• Maksim V. Dmitriev,
• Alexander S. Novikov and
• Andrey N. Maslivets

Beilstein J. Org. Chem. 2024, 20, 2208–2216, doi:10.3762/bjoc.20.188

• -diketones has been developed. The electron-withdrawing power of the heterocyclic substituent (which can be estimated on the basis of calculated Hammett constants) in the 1,3-diketone plays a pivotal role in the studied reaction. The series of meta-hetarylanilines prepared (21–85% isolated yield

• ) demonstrates the synthetic utility of the developed method. Keywords: aniline; benzannulation; condensation; 1,3-diketone; Hammett constants; terphenyl; Introduction The aniline moiety is omnipresent in the synthetic chemistry with applications ranging from building blocks to catalysis [1][2][3][4]. Among

• utilize Hammett constants. Since only a few numbers of experimentally measured Hammett constants for heterocycles are known [55][56], this approach seems unsuitable at first. However, recently, a web-based tool for the calculation of the substituent descriptors compatible with the Hammett sigma constants

Benzothiazolium salts as reagents for the deoxygenative perfluoroalkylthiolation of alcohols

• Armin Ariamajd,
• Nils J. Gerwien,
• Benjamin Schwabe,
• Stefan Dix and
• Matthew N. Hopkinson

Beilstein J. Org. Chem. 2021, 17, 83–88, doi:10.3762/bjoc.17.8

• trifluoromethylthio group (SCF3), for example, is attracting considerable attention due to its strong lipophilicity-enhancing influence (Hansch constant π = 1.44) and electron-withdrawing properties (Hammett constants σp = 0.50 and σm = 0.40) [7][8][9][10][11][12]. On the other hand, longer-chain perfluoroalkylthio

Models of necessity

• Timothy Clark and
• Martin G. Hicks

Beilstein J. Org. Chem. 2020, 16, 1649–1661, doi:10.3762/bjoc.16.137

• ], developing a ML-suitable model for intermolecular interactions is feasible. As noted above, old models such as Gasteiger–Marsili [38][39] charges or Hammett constants [59] have been used in recent applications. This development ignores the immense improvements in hard- and software of the last four decades

Cascade trifluoromethylthiolation and cyclization of N-[(3-aryl)propioloyl]indoles

• Ming-Xi Bi,
• Shuai Liu,
• Yangen Huang,
• Xiu-Hua Xu and
• Feng-Ling Qing

Beilstein J. Org. Chem. 2020, 16, 657–662, doi:10.3762/bjoc.16.62

• SCF3, 0.88 for CF3, and 0.61 for SMe) [1] that helps permeation across biological membranes. Furthermore, the strong electron-withdrawing properties of the SCF3 group (Hammett constants: σp = 0.50, σm = 0.40) [2] with respect to metabolic stability have attracted considerable interest in pharmaceutical

Bioinspired cobalt cubanes with tunable redox potentials for photocatalytic water oxidation and CO₂ reduction

• Zhishan Luo,
• Yidong Hou,
• Jinshui Zhang,
• Sibo Wang and
• Xinchen Wang

Beilstein J. Org. Chem. 2018, 14, 2331–2339, doi:10.3762/bjoc.14.208

• 800 nm and the λmax for 1-R. Correlation of Hammett constants σp for the different ligands with midpoint potentials (E1/2) in complexes 1-R. aCV data for 1-R in MeCN/0.1 M TBAP vs Fc+/Fc under saturated Ar atmosphere. Linear sweep voltammetry of 1-R (0.3 mM) or Co(NO3)2·6H2O (1.2 mM); (a) at a 100 mV

Polysubstituted ferrocenes as tunable redox mediators

• Sven D. Waniek,
• Jan Klett,
• Christoph Förster and
• Katja Heinze

Beilstein J. Org. Chem. 2018, 14, 1004–1015, doi:10.3762/bjoc.14.86

• correlated with the sum of Hammett constants. The 1/1+–4/4+ redox couples are chemically stable under the conditions of electrolysis as demonstrated by IR and UV–vis spectroelectrochemical methods. The energies of the C=O stretching vibrations of the ester moieties and the energies of the UV–vis absorptions

Azobenzene-based inhibitors of human carbonic anhydrase II

• Leander Simon Runtsch,
• David Michael Barber,
• Peter Mayer,
• Michael Groll,
• Dirk Trauner and
• Johannes Broichhagen

Beilstein J. Org. Chem. 2015, 11, 1129–1135, doi:10.3762/bjoc.11.127

• of these findings into account, we conclude that the sulfonamide–zinc interaction dominates the binding affinity. The electronic differences of our azobenzene library is expressed by their absorption spectra (as an indicator for the electron richness of the azobenzene) or in their Hammett constants

• (as an indicator for electron-pushing or pulling effects). When plotted against each other a trend can be observed, which is reflected by a more bathochromic shift when the Hammett constant becomes more negative (Figure 4b). However, when plotting the Hammett constants or the maximal absorbance

• . Inhibition of hCAII by electronically different azobenzene sulfonamides and AAZ. a) Endpoint measurement for the determination of IC50 for compounds 1a–i. b) Hammett constants versus maximal absorbance wavelength shows decreasing trend. c) IC50 versus Hammett constants. d) IC50 versus λmax. Synthesis and