1233146-06-9Relevant academic research and scientific papers
Photo-Induced ortho-C-H Borylation of Arenes through in Situ Generation of Rhodium(II) Ate Complexes
Araujo Dias, Ant?nio Junio,Nagashima, Yuki,Tanaka, Jin,Tanaka, Ken
supporting information, p. 11325 - 11331 (2021/08/03)
Photoinduced in situ "oxidation"of half-sandwich metal complexes to "high-valent"cationic metal complexes has been used to accelerate catalytic reactions. Here, we report the unprecedented photoinduced in situ "reduction"of half-sandwich metal [Rh(III)] complexes to "low-valent"anionic metal [Rh(II)] ate complexes, which facilitate ligand exchange with electron-deficient elements (diboron). This strategy was realized by using a functionalized cyclopentadienyl (CpA3) Rh(III) catalyst we developed, which enabled the basic group-directed room temperature ortho-C-H borylation of arenes.
Rh-catalyzed ortho -selective C-H borylation of N-functionalized arenes with silica-supported bridgehead monophosphine ligands
Kawamorita, Soichiro,Miyazaki, Tatsuya,Ohmiya, Hirohisa,Iwai, Tomohiro,Sawamura, Masaya
, p. 19310 - 19313 (2012/01/15)
Supported phosphine-Rh systems, prepared in situ from silica-supported bridgehead monophosphines and [Rh(OH)(cod)]2, have enabled ortho-selective C-H borylation for a range of arenes containing nitrogen-based directing groups. The regioselectivity was excellent with various N-directing groups, including saturated and unsaturated N-heterocycles, tert-aminoalkyl groups, and imine-type C-N double bonds. The reaction showed significant tolerance toward steric repulsion around the reacting C-H bond. This Rh catalysis complements the Ir-catalyzed ortho-borylation, which is effective for arenes with oxygen-based directing groups.
