Cu(OAc)₂-Mediated Reaction of [60]Fullerene with Aldehydes and Primary Amines for the Synthesis of Fulleropyrrolines

Abstract

The facile one-step reaction of [60]fullerene with aldehydes and primary amines in the presence of cheap and easily available Cu(OAc)·HO afforded a series of new types of fulleropyrrolines with trisubstituted C═C bonds in good to excellent yields, which would be difficult to prepare by known methods. The formed fulleropyrroline under the assistance of Pd(OAc) and CuCl·2HO could be further converted to 1-fulleropyrrolidine by the chlorohydroxylation reaction of C═C bond. Subsequent elimination reaction of 1-fulleropyrrolidine with the aid of TsOH·HO generated the scarce 1-fulleropyrroline derivative.

Synthesis of 2-Aryl-5-alkyl-fulleropyrrolidines: Metal-Free-Mediated Reaction of [60]Fullerene with Aromatic Aldehydes and Inactive Primary Amines

“…The functionalization of fullerenes by using aldehydes and amines is a potential option and has received increasing attention due to their inexpensive price and easily availability. ,, For example, our group reported the Cu­(OAc) 2 ·H 2 O-mediated reaction of C 60 with aliphatic aldehydes and primary amines to generate trisubstituted alkene fulleropyrrolines . The Fe­(ClO 4 ) 3 -mediated reaction of C 60 with arylmethanamines was also reported to afford symmetrical 2,5-diaryl-fulleropyrrolidines .…”

“…Hence, there is still a demand to investigate the reaction of C 60 with aromatic aldehydes and electron-donating amines such as phenethylamines and aliphatic amines to see if the corresponding fulleropyrrolidines are formed because the desired 2-aryl-5-alkyl-fulleropyrrolidines may have a great potential application in the target-directed synthesis of new materials and biologically active compounds. In continuation of our interest in fullerene chemistry, ,− , herein we describe a simple and general method for the synthesis of 2-aryl-5-alkyl-fulleropyrrolidines containing rare 2-aryl-5-benzyl-fulleropyrrolidines via a facile one-step thermal reaction of C 60 with aromatic aldehydes and inactive electron-donating primary amines without the addition of valuable metal salts.…”

DMAP-Mediated Synthesis of Fulleropyrrolines: Reaction of [60]Fullerene with Aromatic Aldehydes and Arylmethanamines in the Absence or Presence of Manganese(III) Acetate

“…This limitation required the functionalization of C 60 with various organic functional groups. , Chemical modification of C 60 induced by transition metal salts instead of traditional peroxide or light have proven to be a powerful tool to functionalize fullerenes, and a large variety of novel fullerene derivatives with structural and functional diversities have been successfully prepared under the assistance of diverse types of transition metal salts. Among the reported transition metal salts, − those from the first-row transition metals, such as Mn­(III), Fe­(III)/Fe­(II), and Cu­(II)/Cu­(I) have been widely used to functionalize fullerenes owing to their low toxicity, easy availability, inexpensive price, and insensitivity to air and water. Although many fullerene reactions catalyzed/promoted by transition metal salts have been developed to functionalize fullerenes, there is still a demand to explore new transition-metal-salt catalyzed/promoted reactions to prepare a plethora of novel fullerene derivatives including the relatively scarce fulleropyrrolines.…”

“…Although many fullerene reactions catalyzed/promoted by transition metal salts have been developed to functionalize fullerenes, there is still a demand to explore new transition-metal-salt catalyzed/promoted reactions to prepare a plethora of novel fullerene derivatives including the relatively scarce fulleropyrrolines. Fulleropyrrolines ,, are generally classified into two categories according to the relative position of nitrogen atom, namely, pyrroline derivatives with/without a nitrogen atom bonding to the fullerene cage directly. Fulleropyrrolines with a directly attached nitrogen atom can be further divided into two groups, that is, 1-fulleropyrrolines with a CN bond and 2-fulleropyrrolines ,, with a CC bond.…”

Copper-Promoted Synthesis of 2-Fulleropyrrolines via Heteroannulation of [60]Fullerene with α-Amino Ketones

“…Free radical reaction, one of the first investigated reactions of fullerenes, represents the most powerful and straightforward protocol for the construction of diversified fullerene derivatives . Particularly, in recent years, transition-metal-catalyzed/promoted radical reactions exhibit excellent ability to create novel functionalized fullerenes, attributed to their remarkable advantages such as high compatibility with a wide range of functional groups. − The transition metals such as Mn­(III), Fe­(II)/Fe­(III), Co(0), Ni(0), Cu­(I)/Cu­(II), Ag­(I), and Pb­(IV) have been continuously utilized to functionalize fullerenes due to their ready availability, cheap price, and ease of manipulation. Despite these advances, further exploration and development of new transition-metal-catalyzed/promoted synthetic methodologies still remain highly demanded for the construction of structurally diversified fullerene derivatives.…”