title: Regioselective borylation of porphyrins by C-H bond activation under iridium catalysis to afford useful building blocks for porphyrin assemblies.
abstract: Highly regioselective and efficient borylation of a variety of porphyrins has been achieved by reaction with bis(pinacolato)diboron through C-H bond activation under iridium catalysis on the basis of the synthetic protocol developed by Miyaura, Hartwig, and Smith. A boryl group can be selectively introduced at sterically uncongested positions in the peripheral aryl groups of porphyrin substrates whose peripheral beta-positions are sterically hindered. Curiously, beta substituents adjacent to the aryl group to be borylated have unexpectedly large effects on the regioselectivity, because the iridium catalyst can discriminate between subtle steric differences. Chemoselective borylation was also achieved for several functionalized porphyrins. This borylation protocol can be applied to various monomeric and oligomeric functional porphyrins, hence offering an efficient route to elaborate multiporphyrin-based molecular constructs.
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, PRESTO & CREST, Japan Science and Technology Agency, Sakyo-ku, Kyoto 606-8502, Japan.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Hata
authors.forename: Shigeru
authors.initials: S
authors.lastname: Yamaguchi
authors.forename: Goro
authors.initials: G
authors.lastname: Mori
authors.forename: Satomi
authors.initials: S
authors.lastname: Nakazono
authors.forename: Taisuke
authors.initials: T
authors.lastname: Katoh
authors.forename: Keishi
authors.initials: K
authors.lastname: Takatsu
authors.forename: Satoru
authors.initials: S
authors.lastname: Hiroto
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Shinokubo
authors.forename: Atsuhiro
authors.initials: A
authors.lastname: Osuka