Triphenylsilane‐fused Porphyrins |
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| Authors: | Kenichi Kato Jun Oh Kim Prof. Dr. Hideki Yorimitsu Prof. Dr. Dongho Kim Prof. Dr. Atsuhiro Osuka |
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| Affiliation: | 1. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, Japan;2. Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, Korea;3. (+81)?75‐753‐3970 |
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| Abstract: | 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. |
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| Keywords: | electrophilic substitution fused-ring systems porphyrinoids sila-Friedel– Crafts reaction silicon |
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