A Mild and General Method for the Synthesis of 5-Substituted and 5,5-Disubstituted Fulleroprolines

Abstract

The reductive ring-opening of fullerenyldihydropyrrole yields ethyl N-benzhydryl fullerenyl[60]glycinate, which is deprotected to give ethyl fullerenylglycinate. The free amine is able to react with a variety of aldehydes and ketones in a Mannich-type process to produce 5-substituted and 5,5-disubstituted fulleroprolines and represents a versatile and general strategy to this class of compounds.

[60]Fullerenyl amino acids and peptides: a review of their synthesis and applications

“…This diacid 25 has been used to synthesise potential biologically useful fullerene amino acid derivatives. 9 BF 3 $Et 2 O and NaCNBH 3 mediated reductive ring-opening of the dihydrofullerenoproline derivative 8b 26 yields ethyl N-benzhydrylfullerenyl[60]glycinate 27, which was N-deprotected to give ethyl fullerenylglycinate 10 28, a true fullerenyl a-amino ester, which was fully characterized as its more stable N-acetyl derivative 29. Therefore, the original structure 26 could be considered as a protected version of 28.…”

Synthesis of Fullerooxazoles: Novel Reactions of [60]Fullerene with Nitriles Promoted by Ferric Perchlorate

“…Diverse types of organic molecules have been utilized as starting materials in fullerene chemistry. For example, the reactions of [60]fullerene (C 60 ) with various aldehyes and ketones, , 1,3-dicarbonyl compounds such as malonate esters, , β-keto esters, , and β-diketones, ,, and carboxylic acid derivatives such as carboxylic acids, carboxylic anhydrides, and malonic acids give a diversity of fullerene products that incorporate with the desired different structural motifs. Although numerous reactants have been employed to the reactions with C 60 , the reactions of nitriles with C 60 have been seldom explored.…”

Individual (f,tA)‐ and (f,tC)‐Fullerene‐Based Nickel(II) Glycinates: Protected Chiral Amino Acids Directly Linked to a Chiral π‐Electron System

“…These compounds are of either a di‐ or trialkylamino‐acid type, and decreases the functionality of the amino group. The only example of a deprotected primary amino acid directly linked to a fullerene cage, through only the α‐carbon atom, is racemic ethyl fullerenyl[60]glycinate, which was isolated but not fully characterized because of fast precipitation from the solution …”