Decatungstate-Photocatalyzed Addition of Lactones to [60]Fullerene

Abstract

A new, one step functionalization of C60 with lactones has been developed. This photochemical approach utilizes a variety of lactonyl radicals deriving from lactones through a hydrogen atom abstraction process mediated by tetrabutylammonium decatungstate [(n-Bu4N)4W10O32]. This reaction provides access to a previously unknown class of materials, namely 1-lactonyl-2-hydro[60]­fullerenes. A mechanism for this new reaction has been proposed based mainly on the structure of reaction products and deuterium-incorporated experiments.

Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C–H Bonds Elaboration

“…The decatungstate-photocatalyzed functionalization of [60]fullerene with lactones was devised (compare section 2.8). 533 The photocatalyzed C(sp 3 )−H sulfinylation 534 or C(sp 3 )−H/C(sp 2 )−H trifluoromethylthiolation 535 for the forging of C−S bonds have been obtained (compare section 3.3).…”

Decatungstate‐Photocatalyzed Acylation of Single‐Walled Carbon Nanotubes

“…[8] The catalytic activity of TBADT, once photoexcited, regards its deep highest occupied molecular orbital (HOMO) at −7.13 eV, which is able to accept hydrogen atoms even from light alkanes, e.g., methane with hydrogen atom dissociation energy 4.55 eV, [11] thus being extremely easy to occur for other organic moieties such as aldehydes. [12] Notably, a few monoadducts of C 60 derived by radical addition of substituted toluenes and anisoles, [13] aldehydes, [14] ethers, [15] alcohols, [16] and lactones [17] with TBADT as photocatalyst have been reported. In the decatungstate-photocatalyzed acylation of C 60 , the HOMO and lowest unoccupied molecular orbital energy levels of C 60 (−5.87 and −4.18 eV, respectively) [18] Although the functionalization and modification of single-walled carbon nanotubes (SWCNTs) has been advanced for two decades, their chemical transformation via catalytic processes has yet to be explored and further facilitate their industrial utility.…”

NHC-Catalyzed Three-Component Hydroalkylation Reactions of [60]Fullerene: An Umpolung Approach to Diverse Monoalkylated Hydrofullerenes

“…However, few methods have been described on the preparation of monoalkylated hydrofullerenes. The conventional synthetic approaches involve the nucleophilic additions of organometallic reagents and photoinduced radical additions. , Recently, transition-metal-catalyzed/promoted radical reactions have also been developed by the groups of Jin and Yamamoto, and Wang . Notwithstanding these impressive achievements, the catalytic hydroalkylation of [60]­fullerene remains scarce. , Furthermore, low selectivity, narrow substrate scope, and poor functional group tolerance are usually encountered in the majority of the aforementioned transformations.…”