Triphenylsilane-fused Porphyrins

A reaction sequence of 2‐(diphenylsilyl)phenylation by Negishi coupling and intramolecular sila‐Friedel–Crafts reaction has been explored for the synthesis of mono‐triphenylsilane‐fused porphyrins 5 M and 6 M (M= Ni, Zn) and bis‐triphenylsilane‐fused porphyrins 7 M and 8 Ni. A triply linked tripheny...

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Bibliographic Details
Published in:Chemistry, an Asian journal an Asian journal, 2016-06, Vol.11 (11), p.1738-1746
Main Authors: Kato, Kenichi, Kim, Jun Oh, Yorimitsu, Hideki, Kim, Dongho, Osuka, Atsuhiro
Format: Article
Language:English
Subjects:
Chemistry
electrophilic substitution
fused-ring systems
porphyrinoids
sila-Friedel-Crafts reaction
silicon
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Summary:A reaction sequence of 2‐(diphenylsilyl)phenylation by Negishi coupling and intramolecular sila‐Friedel–Crafts reaction has been explored for the synthesis of mono‐triphenylsilane‐fused porphyrins 5 M and 6 M (M= Ni, Zn) and bis‐triphenylsilane‐fused porphyrins 7 M and 8 Ni. A triply linked triphenylsilane‐fused NiII porphyrin, 13 Ni, was synthesized in a stepwise manner involving the above reaction sequence and a final Pd‐catalyzed C−H activating arylative cyclization. The silicon atom in 13 Ni takes a distorted planarized structure with an almost perpendicular Si‐phenyl group, causing an electronic effect due to effective σ*–π* interaction. Friedel‐Craftsmanship: Triphenylsilane‐fused porphyrins were synthesized via Negishi coupling and subsequent intramolecular sila‐Friedel–Crafts reactions. Triply linked triphenylsilane‐fused NiII porphyrin takes a distorted planarized structure with an almost perpendicular Si‐phenyl group, providing an effective electronic effect due to σ*–π* conjugation.
ISSN:1861-4728
1861-471X
DOI:10.1002/asia.201600424