Efficient synthesis of fluorinated triphenylenes with enhanced arene–perfluoroarene interactions in columnar mesophases

• Yang Chen,
• Jiao He,
• Hang Lin,
• Hai-Feng Wang,
• Ping Hu,
• Bi-Qin Wang,
• Ke-Qing Zhao and
• Bertrand Donnio

Beilstein J. Org. Chem. 2024, 20, 3263–3273, doi:10.3762/bjoc.20.270

• intermolecular slipped J-type aggregation, supported by S/WAXS and proposed the model of Colrec mesophase [55][56][57]. DFT computation For a deeper understanding of the electronic properties of these fluorine triphenylenes, we performed some DFT computation of F1 and G11 with the shortest methyl chain, and the

Solving the puzzling competition of the thermal C²–C⁶ vs Myers–Saito cyclization of enyne-carbodiimides

• Anup Rana,
• Mehmet Emin Cinar,
• Debabrata Samanta and
• Michael Schmittel

Beilstein J. Org. Chem. 2016, 12, 43–49, doi:10.3762/bjoc.12.6

• pathway if the trapping reaction by hydrogen transfer is no more rate determining. Keywords: DFT computation; diradical; enyne-carbodiimides; hydrogen transfer; thermal cyclization; Introduction The thermal cyclizations of enediynes [1][2][3][4][5][6], enediallenes [7][8][9][10], bisallenes [11], enyne

Interplay of ortho- with spiro-cyclisation during iminyl radical closures onto arenes and heteroarenes

• Roy T. McBurney and
• John C. Walton

Beilstein J. Org. Chem. 2013, 9, 1083–1092, doi:10.3762/bjoc.9.120

• resolved spectra only at 230–235 K (Figure 3). The corresponding benzofuranyl-iminyl was not detectable at 230 K or above. The EPR hfs obtained from simulation of the spectrum (Table 2) show this to be a benzyl type radical and we assign it structure 12a (Scheme 2). A DFT computation for 12a at the UB3LYP

• the tert-butyl substituent of the solvent. It is known that ArCMe=N• type radicals do not add to t-BuPh under EPR conditions [19][37] neither do EtO• radicals (from dissociation of 6), and hence, we assign this spectrum to the ethoxycarbonyloxyl adduct 9a. This identification was supported by a DFT

• computation [38] that gave hfs in close agreement with experiment (Table 1). This was a surprising result because previously the only radicals of type 9 that had been spectroscopically detected had resulted from additions of phenyl [34] or bridgehead radicals (bicyclo[2.2.2]oct-1-yl and adamantyl) [39]. These

EPR and pulsed ENDOR study of intermediates from reactions of aromatic azides with group 13 metal trichlorides

• Giorgio Bencivenni,
• Riccardo Cesari,
• Daniele Nanni,
• Hassane El Mkami and
• John C. Walton

Beilstein J. Org. Chem. 2010, 6, 713–725, doi:10.3762/bjoc.6.84

• +•, containing a single F-atom. The DFT computation on the dimer hfs gave satisfactory agreement (Table 1), with the possible exception of the para-F hfs. However, DFT-computed a(F) values varied from 7.2, to 7.1, to 9.5 and 4.3 G with 6-31G(d), 6-31+G(d,p), DGDZVP and 6-311++G(d,p) basis sets, respectively