Organic Chemistry Laboratory, Nagoya University

Masakazu Nambo, Yasutomo Segawa, Atsushi Wakamiya, and Kenichiro Itami

Chem. Asian J. Early View DOI: 10.1002/asia.201000583

Hydroarylation of Fullerene by Rhodium Catalyst

A Rh-catalyzed reaction of C₆₀ and C₇₀ with organoboron compounds is described. This new catalytic method enables introduction of various organic groups onto C₆₀ and C₇₀. [Rh(cod)(MeCN)₂]BF₄ proved to be the most effective catalyst in terms of productivity and selectivity. The reaction generally proceeds with a high regioselectivity and in a mono-addition selective manner. It was found that water is an essential additive to promote the reaction. By X-ray crystal structure analysis, we have confirmed the reaction site of organometallic-based hydroarylation of C₇₀ for the first time. Various functional fullerenes, such as fullerene-tagged amino acids and fullerene-capped π systems, can be synthesized. The X-ray crystal structure of biphenyl-attached C₆₀ revealed an interesting opportunity for the well-organized alignment of bucky balls by taking advantage of CH–π interactions.