Mechanistic studies of the solvolysis of alkanesulfonyl and arenesulfonyl halides

• Malcolm J. D’Souza and
• Dennis N. Kevill

Beilstein J. Org. Chem. 2022, 18, 120–132, doi:10.3762/bjoc.18.13

• . The solvolyses of these additional types of sulfur(VI) substrates will be the topics of a future review. Keywords: correlation; Grunwald–Winstein equation; Hammett equation; mechanism; solvolysis; sulfonyl halides; Review 1. Introduction to solvolyses of sulfonyl halides In medicinal chemistry

• to synchronous bond-making and bond-breaking, with a small negative charge development on the sulfur at the transition state, for the solvolytic process. Subsequent to this 1927 study, Hammett reported [5][6] in 1937, the development of the Hammett equation, involving the consideration of a scale

• of the review, the study is of solvolysis mechanisms and the reactions involve the solvolyses of a series of para and meta-ring-substituted substrates. Applying the Hammett equation to the rate measurements of Berger and Oliver [4], we arrive, in 50% water/50% acetone (v/v) at a reaction constant ρ

Cathodic hydrodimerization of nitroolefins

• Michael Weßling and
• Hans J. Schäfer

Beilstein J. Org. Chem. 2015, 11, 1163–1174, doi:10.3762/bjoc.11.131

• nitroolefins can be qualitatively seen. Aryl substituents shift the potentials to more negative values according to their Hammett σ values [28]: 10 (4-CF3, σp = 0.53) > 1 (4-H, σp = 0) > 9 (4-CH3O, σp = −0.12). With a Hammett equation for an electrochemical reaction and using the Ep values as E0-values one

• . For the other substituents no σ-values are available to apply the Hammett equation. They are ordered according to decreasing Ep-values in three groups: 11 (2-furyl) > 9 (4-CH3O) > 12 (2-pyrrolyl); 14 (two o-Cl) ≈ 13 (one o-Cl) > 15 (two o-F); another correlation concerns the vinyl substituents at C2

Oxidative 3,3,3-trifluoropropylation of arylaldehydes

• Akari Ikeda,
• Masaaki Omote,
• Shiho Nomura,
• Miyuu Tanaka,
• Atsushi Tarui,
• Kazuyuki Sato and
• Akira Ando

Beilstein J. Org. Chem. 2013, 9, 2417–2421, doi:10.3762/bjoc.9.279

• substantially. p-Methyl and p-methoxybenzaldehydes gave 3h and 3i in 26% and 17% yield, respectively (Table 2, entries 7 and 8). meta-Substitution of benzaldehyde with a methoxy group gave 3j in 58% yield (Table 2, entry 9). These results are in accordance with the Hammett equation. ortho-Substitution of