Journal Article Peripherally Silylated Porphyrins.

Kato, Kenichi  ,  Fujimoto, Keisuke  ,  Yorimitsu, Hideki  ,  Osuka, Atsuhiro

21 ( 39 )  , pp.13522 - 13525 , 2015-09-21 , wiley
Article first published online: 19 AUG 2015
Silylation of peripherally lithiated porphyrins with silyl electrophiles has realized the first synthesis of a series of directly silyl-substituted porphyrins. The meso-silyl group underwent facile protodesilylation, whereas the β-silyl group was entirely compatible with standard work-up and purification on silica gel. The meso-silyl group caused larger substituent effects to the porphyrin compared with the β-silyl group. Silylation of β-lithiated porphyrins with 1, 2-dichlorodisilane furnished β-to-β disilane-bridged porphyrin dimers. A doubly β-to-β disilane-bridged Ni(II)-porphyrin dimer was also synthesized from a β, β-dilithiated Ni(II)-porphyrin and characterized by X-ray crystallographic analysis to take a steplike structure favorable for interporphyrinic interaction. Denickelation of β-silylporphyrins was achieved upon treatment with a 4-tolylmagnesium bromide to yield the corresponding freebase porphyrins.

Number of accesses :  

Other information