Premium
Rhodium‐Catalyzed Synthesis and Optical Properties of Silicon‐Bridged Arylpyridines
Author(s) -
Shintani Ryo,
Misawa Nana,
Takano Ryo,
Nozaki Kyoko
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201605000
Subject(s) - cycloaddition , chemistry , rhodium , regioselectivity , catalysis , substituent , pyridine , protonation , ring (chemistry) , silicon , chirality (physics) , alkylation , photochemistry , medicinal chemistry , stereochemistry , organic chemistry , ion , chiral symmetry breaking , physics , quantum mechanics , nambu–jona lasinio model , quark
Abstract A convergent and regioselective synthesis of silicon‐bridged 4‐arylpyridines has been developed through a rhodium‐catalyzed [2+2+2] cycloaddition of silicon‐containing diynes with nitriles. The absorption and emission properties of these compounds have been examined and could be tuned by varying the substituent on the benzene ring, as well as through the protonation or alkylation of the nitrogen atom on the pyridine ring. A catalytic asymmetric synthesis of silicon‐centered axially chiral spirocyclic derivatives has also been achieved with high enantioselectivity by using a newly modified MeO‐MOP (MeO‐MOP=2‐(diphenylphosphino)‐2′‐methoxy‐1,1′‐binaphthyl) derivative as the chiral ligand. These spirocyclic compounds were found to be CPL‐active (CPL=circularly polarized luminescence), representing the first CPL‐active compounds based on the chirality at silicon.