Facile access to amino-substituted cyclopentafullerenes: novel reaction of [60]fullerene with β-substituted propionaldehydes and secondary amines in the absence/presence of magnesium perchlorate

Abstract

A series of scarce amino-substituted cyclopentafullerenes instead of the expected N-alkyl-2,5-disubstituted fulleropyrrolidines were synthesized in moderate to excellent yields via the simple one-step reaction of [60]fullerene with cheap and easily available β-substituted propionaldehydes and secondary amines in the absence/presence of magnesium perchlorate. The in situ generation of allylic amines from β-substituted propionaldehydes and secondary amines played a crucial role in the successful preparation of amino-substituted cyclopentafullerenes without additional carbons. With the addition of magnesium perchlorate, secondary amines containing ethyl group(s) could produce novel amino-substituted cyclopentafullerenes with two additional carbons. All the obtained cyclopentafullerenes displayed high stereoselectivity with cis isomers as the exclusive or major products. Plausible reaction mechanisms are proposed to elucidate the above-mentioned reaction process.