Peripherally Silylated Porphyrins.

• Kato, Kenichi

• Fujimoto, Keisuke

• Yorimitsu, Hideki

• Osuka, Atsuhiro

Abstract

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.

Article first published online: 19 AUG 2015

Journal

• Chemistry - A European Journal

  Chemistry - A European Journal 21 (39), 13522-13525, 2015-09-21

  wiley

Keywords

• lithiation
• porphyrin
• porphyrin dimer
• silylation
• substituent effects

Details

• CRID: 1050282810795522688
• NII Article ID: 120005678166
• NII Book ID: AA11076269
• ISSN: 09476539
• ISSN: 15213765
• DOI: 10.1002/chem.201502563
• HANDLE: 2433/202570
• Web Site: https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fchem.201502563
• Web Site: https://onlinelibrary.wiley.com/doi/full/10.1002/chem.201502563
• Text Lang: en
• Article Type: journal article
• Data Source:
  • IRDB
  • Crossref
  • CiNii Articles
  • KAKEN