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Additive‐Controlled Switchable Selectivity from Cyanobenzenes to 2‐Alkynylpyridines: Ruthenium(II)‐Catalyzed [2+2+2] Cycloadditions of Diynes and Alkynylnitriles
Author(s) -
Bhatt Divya,
Patel Neha,
Chowdhury Hrishikesh,
Bharatam Prasad V.,
Goswami Avijit
Publication year - 2018
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201800228
Subject(s) - chemistry , ruthenium , cationic polymerization , catalysis , selectivity , dimethoxyethane , combinatorial chemistry , photochemistry , medicinal chemistry , organic chemistry , electrode , electrolyte
A highly efficient additive‐dependent chemoselective protocol for the synthesis of fused cyanoarenes and 2‐alkynylpyridines has been developed by the reaction of 1,6‐diynes with alkynylnitriles using chloro(pentamethylcyclopentadienyl) (cyclooctadiyne)ruthenium(II) as catalyst in dimethoxyethane (DME). The course of the reaction can be drastically altered simply by adding a catalytic amount of AgOTf as an additive resulting in a comprehensive shift in product formation from cyanoarenes to 2‐alkynylpyridines. Theoretical studies clearly indicate that the neutral Ru‐complex is responsible for the formation of cyanobenzenes, whereas the in situ generated cationic Ru‐complex plays a crucial role in the 2‐alkynylpyridines formation.