Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 24, Issue 42, Pages 10653-10661Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201802298
Keywords
catalysis; cycloaddition reactions; DFT calculations; open-cage fullerenes; rhodium
Categories
Funding
- Spanish Ministry of Economy and Competitivity (MINECO) [CTQ2017-85341-P, CTQ2017-83587-P, RYC2012-11112]
- Generalitat de Catalunya [2017-SGR-39]
- EU under the FEDER [UNGI10-4E-801]
Ask authors/readers for more resources
A novel methodology to transform C-60 into a variety of open-cage fullerene derivatives by employing rhodium(I) catalysis has been developed. This transformation encompasses a partially intermolecular [2+2+2] cycloaddition reaction between diynes 1 and C-60 to deliver a cyclohexadiene-fused fullerene, which concomitantly undergoes a formal [4+4]/retro-[2+2+2] rearrangement to deliver open-cage fullerenes 2. Most notably, this process occurs without the need of photoexcitation. The complete mechanism of this transformation has been rationalized by DFT calculations, which indicate that, after [2+2+2] cycloaddition, the cyclohexadiene-fused intermediate evolves into the final product through a Rh-catalyzed di-pi-methane rearrangement followed by a retro-[2+2+2] cycloaddition. The obtained open-cage fullerenes can be derivatized by Suzuki-Miyaura cross-coupling or subjected to ring expansion to deliver a 12-membered ring orifice in the fullerene structure. Overall, the methodology presented constitutes a straightforward entry to functional open-cage C-60 fullerene derivatives by employing catalytic methods.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available