It has recently been pointed out that current density functionals are inaccurate for computing stereoelectronic effects and energy differences of isomerization reactions and isodesmic reactions involving alkanes; this has been interpreted as an incorrect prediction of medium-range correlation energies. This letter shows that the recently published M05-2X functional has good accuracy for all thr...

Stereoelectronic effects modulate molecular structure, reactivity, and conformation. We find that the interaction between the ester and carboxyl moieties of aspirin has a previously unappreciated quantum mechanical character that arises from the delocalization of an electron pair (n) of a donor group into the antibonding orbital (π*) of an acceptor group. This interaction affects the physicoche...

Computations involving the cyclization of the 5-hexenyl radical to produce methylcyclopentane (81%), 1-hexene (17%), and cyclohexane (2%) as a result, proved that the reaction is kinetically rather than thermodynamically controlled. Specifically the stereoelectronic requirement of the addition of the radical center to the alkene in the transition state is the underlying factor of the difference...

The structure of phenylcyclopropane radical cation (1•+, R ) H) is derived from CIDNP effects observed during the electron transfer reaction of 1 with chloranil. This species is an example of an elusive structure type. The secondary cyclopropane protons show significantly divergent hyperfine coupling constants due to an unprecedented stereoelectronic effect. Incorporation into a redox-active pe...

A chlorosilane elimination reaction has been developed that allows the efficient synthesis of optically pure C1-symmetric, C1-backboned diphosphines with a wide variety of stereoelectronic characteristics.

Correction for ‘Stereoelectronic power of oxygen in control chemical reactivity: the anomeric effect is not alone’ by Igor V. Alabugin et al. , Chem. Soc. Rev. 2021, DOI: 10.1039/d1cs00386k.