Reductive Decarbonylation of a Cage-Opened C₆₀ Derivative

Abstract

The decarbonylation of a cage-opened C 60 derivative was examined by employing single-electron reductants. During the reaction, an H 2 O molecule was spontaneously encapsulated inside the cage (up to 78%) through the thus-formed 14membered-ring orifice even though the H 2 O encapsulation had long been considered to require an orifice consisting of at least 16 atoms. The crystallographic analysis revealed an orifice shape closer to a circle which significantly contributes to the decreased activation barrier for the H 2 O encapsulation.Letter pubs.acs.org/OrgLett

Near‐Infrared‐Absorbing Chiral Open [60]Fullerenes

“…As the results, 3 a was found to be obtained, whose structure was determined by NMR and MS analysis. This compound is considered to be formed from 2 a by cleaving the C(1)−C(2) bond, thus increasing the ring‐atom count [25a] from 12 to 16 on the orifice. This is the first carbene‐mediated orifice expansion of an open [60]fullerene.…”

“…In the presence of S 8 , the formation of sulfide derivative 4 a was inevitable where the S atom was inserted between the C(2)À C(3) bond (Figure 2a). [25] When sulfur scavengers such as 5 a, [26] 6 a, [27] and 7, [28,29] which have higher reactivity than 1 a against S 8 , were employed, the yield of 3 a was improved up to 23 %.…”

π-Extended Fullerenes with a Reactant Inside

“…Herein, we report a novel methodology to provide π-extended fullerenes accompanied by the encapsulation of in situ generated NH 3 (Figure ). We also showcase that the pre-encapsulated NH 3 molecule undergoes timed orifice-expansion, achieving the construction of a huge orifice with a ring-atom count of 19.…”

“…The condensation reaction of 1 and diamine gives B which would be converted into an enol form associated with the destruction of the aromaticity. The enol form of B then underwent hydrolysis to give quinone and NH 3 together with C which changes into D and 4 via disproportionation. , Notably, phenanthrenequinone is known to undergo a unique self-condensation reaction to give an isoimide derivative in the presence of ammonium acetate . Thus, we anticipated that the formation of quinone and NH 3 is a driving force to afford imidazole-containing π-extended fullerenes 3 (Figure c).…”

Phosphorus ylides of cage-opened sulphide [60]fullerene derivatives

“…As a result, 3b and 3c were obtained in 22 and 39% isolated yields, respectively. While the decarbonylation 13 of 3b did not occur at 180 °C for 15 min, it effectively proceeded in the presence of TDAE, giving 3c in 77% yield (Scheme 1b). This reductive decarbonylation was inevitable by shortening the reaction time or decreasing the temperature so that 3b and 3c were always obtained together.…”