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A novel generation of 7-aryl phenothiazinyl substituted polyacetylenes is readily accessible controlled rhodium-catalyzed polymerization of the corresponding 3-ethynyl 7-aryl phenothiazines. The monomers are synthesized by Suzuki coupling, Heck coupling, or Buchwald-Hartwig amination, and Bestmann-Ohira reaction. This allows for the introduction of electron donating and releasing substituents with different ligation patterns.

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The ruthenium(II)-catalyzed regioselective annulation of -(7-azaindole)amides with 1,3-diynes has been demonstrated. Bioactive -amino-7-azaindole has been used as a new bidentate directing group to furnish an array of 3-alkynylated isoquinolones. Furthermore, the developed protocol works efficiently for both aryl- and heteroaryl-substituted amides producing a range of pharmacologically useful 7-azaindole-based isoquinolones with a wide range of functionality.

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A co-operative Ni-Cu system for Csp-Csp and Csp-Csp(2) cross-coupling providing a direct access to unsymmetrical 1,3-diynes and en-ynes.

Chem Commun (Camb)

December 2014

Department of Organic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, India.

An efficient cross-coupling of alkynes with alkynyl and alkenyl halides catalysed by a Ni-Cu system without any ligand has been achieved. The reaction is suggested to proceed by Ni(0) catalysis assisted by Cu(I). A series of functionalised diaryl, aryl-alkyl, aryl-heteroaryl, diheteroaryl 1,3-di-ynes and en-ynes are obtained in high yields.

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