Theoretical Study of the Electronic Effects in the Intramolecular Ketene-Styrene [2+2] Cycloaddition

DFT (B3LYP/6-31+G*) and post-Hartree-Fock (MP2/6-31+G*//B3LYP/6-31G*) calculations were carried out in order to explain the effect of a remote substituent in the intramolecular ketene-styrene [2+2] cycloaddition of p-substituted 2-methyl-7-arylhepta- 1,6-dien-1-one which produces the bicycle[3.1.1] or the bicycle [3.2.0] heptanones according to Bèlanger experimental results. The transition state geometries were found as an asynchronous process with a three-member ring structure and an incipient positive charge development. Kinetic and thermodynamic controls were proposed at B3LYP/6-31+G* to determine which product is most likely to form in a competence reaction. In addition, the value of the ρ experimental reaction constant was reproduced, ρ ~ -1.34.

Identification of the first enantiopure Rac1–Tiam1 protein–protein interaction inhibitor and its optimized synthesis via phosphine free remote group directed hydroarylation

The remote substituent regiocontrol of phosphine free Heck hydroarylation has been exploited for the preparation of the first enantiopure inhibitor of Rac1–Tiam1 PPI.

Photochemical Transformation of some 3-benzyloxy-2-(benzo[b]thiophen-2-yl)-4Hchromen-4-ones: A Remote Substituent Effect

The effect on photochemical transformations of the substituents present remotely from the reaction site in 3-benzyloxy-2-(benzo[b]thiophen-2-yl)-4H-chromen-4-ones has been determined. The structure(s) of the substrates and photoproducts were established by spectroscopic techniques (UV, IR, and NMR). The substituents had profound effects on product yield and distribution. Electron withdrawing groups (EWGs) on the benzenoid moiety of the chromenone nucleus increased the yield of the photoproducts whereas electron donating groups (EDGs) decreased the yield. These results may be attributed to “state switching” of the substituents during excitation.

Nickel(ii) pincer complexes demonstrate that the remote substituent controls catalytic carbon dioxide reduction

New pincers containing a pyridinol ring form active nickel catalysts for CO2 reduction, and interestingly protonation switches the catalyst off.

New azo-decorated N-pyrrolidinylthiazoles: synthesis, properties and an unexpected remote substituent effect transmission

A series of new 5-azo substituted derivatives from 2-N-pyrrolidinylthiazole show an hindered rotation around the C2–N bond in good correlation with the sigma constants of the substituents on the ‘remote’ benzene ring.