Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivity

In this study, the thermal reaction of the La@C2v-C82 anion with benzyl bromide derivatives 1 at 110 °C afforded single-bonded adducts 2–5 with high regioselectivity. The products were characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and visible–near infrared spectroscopy. The reaction of La@C2v-C82 with alkyl halides using the same conditions showed no consumption of La@C2v-C82, indicating that the reactivity of La@C2v-C82 toward alkyl halides was effectively increased by one-electron reduction. Single-crystal X-ray diffraction analysis of the single-bonded adduct 3a revealed the addition site of the p-methoxybenzyl group on La@C2v-C82. Theoretical calculations indicated that the addition site carbons in neutral La@C2v-C82 have high spin density, whereas those in the La@C2v-C82 anion do not have high charge densities. Thus, the reaction is believed to occur via electron transfer, followed by the radical coupling of La@C2v-C82 and benzyl radicals, rather than by bimolecular nucleophilic substitution reaction of La@C2v-C82 anion with 1.

Beilstein J. Org. Chem. 2023, 19, 1858–1866. doi:10.3762/bjoc.19.138

Source: Beilstein Journal of Organic Chemistry - December 11, 2023 Category: Chemistry Authors: Beilstein Journal of Organic Chemistry - Syndicated Feeds Tags: electron transfer metallofullerene radical reduction Full Research Paper Source Type: research