911835-77-3Relevant academic research and scientific papers
Preparation of meso-silylporphyrins via nickel-catalyzed coupling of meso-brominated Ni(II) porphyrins with silylzinc reagents
Hayashi, Satoshi,Endo, Taiga,Takanami, Toshikatsu
, p. 1082 - 1098 (2019/07/31)
– In this paper, we developed a technique for the nickel-catalyzed coupling of meso-brominated Ni(II) porphyrins with silylzinc reagents in order to prepare meso-silyl-substituted Ni(II) porphyrins. Porphyrin silylation occurs under mild conditions and ex
Porphyrinylboranes Synthesized via Porphyrinyllithiums
Fujimoto, Keisuke,Yorimitsu, Hideki,Osuka, Atsuhiro
supporting information, p. 11311 - 11314 (2015/08/03)
As the most nucleophilic porphyrins, meso- or β-lithiated porphyrins were generated by iodine-lithium exchange reactions of the corresponding iodoporphyrins with n-butyllithium at -98°C. Porphyrinyllithiums thus prepared were used for synthesis of dimesitylporphyrinylboranes through reactions with fluorodimesitylborane. The boryl groups proved to serve as an electron-accepting unit to alter the photophysical and electrochemical properties. In addition, 5-diarylamino-15-dimesitylboryl-substituted donor-accepter porphyrins showed increased intramolecular charge-transfer character in the S1 state. Furthermore, the reaction of β-lithiated porphyrin with dichloromesitylborane provided a boron-bridged porphyrin dimer, which exhibited a conjugative interaction between two porphyrin units through the vacant p-orbital on the boron center. Porphyrinyllithiums were generated by iodine-lithium exchange of the corresponding iodoporphyrins. The porphyrinyllithiums were useful for the synthesis of a series of porphyrinylboranes through reactions with suitable haloboranes. The boryl groups served as electron-accepting units to alter the photophysical and electrochemical properties. A B,N-substituted donor-accepter porphyrin showed an increased intramolecular charge-transfer character in the S1 state. A boron-bridged porphyrin dimer exhibited a conjugative interaction between two porphyrin units through the vacant p-orbital at the boron atom.
Silylethynyl substituents as porphyrin protecting groups for solubilization and selectivity control
Oda, Kazuma,Akita, Masanari,Hiroto, Satoru,Shinokubo, Hiroshi
, p. 1818 - 1821 (2014/04/17)
Silylethynyl substituents are proposed as protecting groups for porphyrin derivatives to enhance their solubility and enable regioselective functionalization. After usage as protecting groups, silylethynyl groups at the meso-positions can be efficiently removed upon heating with aqueous H 2SO4 in the presence of a surfactant. This approach was applied to the preparation of unsymmetrically β-substituted porphyrins and porphin-porphyrin oligomers, which were inaccessible by conventional methods.
