Easy Access to [60]Fulleroalkaloids via Photoinduced Reactions of Tertiary Amines with [60]Fullerene

Abstract

Photoinduced reactions of tertiary amines with [60]fullerene (C60) were successfully applied to the synthesis of [60]fulleroalkaloids. This method is easy and effective for constructing C60 derivatives containing natural alkaloids for the purpose of checking the influence of the carbon cage on the biological activities of the alkaloids. In this letter, the preparation and characterization of [60]fulleroscandine is reported.

Structural Aspects of Fullerene ChemistryA Journey through Fullerene Chirality

“…Another multianellated C(1),C(2),C(9),C(12)-adduct of C 60 , 342 (Scheme ) including a noninherently chiral addition pattern as well as a multitude of stereogenic centers in the addend moiety, was obtained in a diastereoselective tandem reaction between the alkaloid scandine ( 343 ) and C 60 . The sequence includes a photoinduced addition of the tertiary amine subunit of the alkaloid and a [2 + 2] cycloaddition of the pendant vinyl group to the adjacent formal double bond of the fullerene.…”

Alkaloid−Fullerene Systems through Photocycloaddition Reactions1

“…As expected, a very obvious [M + Ag] + ion peak appeared at m / z 1177, further confirming the identity of the molecular ion peak. In our previous paper, the proposed structure of 4a was confirmed by UV−vis, FT-IR, TOF-SIMS, 1 H NMR, and 13 C NMR and further substantiated by HMQC, HMBC, and ROESY spectra. Interestingly, the path to 4a involves a [2 + 2] cycloaddition between the vinyl group and the C 60 double bond adjacent to the previously formed ring connection.…”

“…Compound 4a . Its UV−vis, FT-IR, TOF-SIMS, 1 H NMR, and 13 C NMR spectral data have been described elsewhere …”

“…However, little attention has been directed toward expanding this type of reaction toward more complex photoadducts. We have recently reported that scandine 1a adds directly to C 60 under irradiation to form a novel C 60 adduct . Herein, we report further investigations resulting in the synthesis of scandine-, 10-hydroxyscandine-, tazettine-, and gramine-containing [60]fullerenes.…”