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.
Bibliographical noteFunding Information:
The work at Kyoto was supported by Grants-in-Aid from MEXT (No.: 25107002 “Science of Atomic Layers”) and from JSPS (No.: 25220802 (Scientific Research (S)), 24685007 (Young Scientists (A)), 26620081 (Exploratory Research)) and by ACT-C, JST. H.Y. thanks Kansai Research Foundation for Technology Promotion and The Asahi Glass Foundation for financial support. The research at Yonsei University was supported by the Global Research Laboratory (GRL) Program (2013K1A1A2A02050183) of the Ministry of Education, Science and Technology (MEST) of Korea.
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All Science Journal Classification (ASJC) codes
- Organic Chemistry