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Chem Sci. 2018 Dec 19;10(7):2193-2198. doi: 10.1039/c8sc04610g. eCollection 2019 Feb 21.

Cobalt-bridged secondary building units in a titanium metal-organic framework catalyze cascade reduction of N-heteroarenes.

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Department of Chemistry , University of Chicago , 929 E. 57th St. , Chicago , Illinois 60637 , USA . Email:
College of Chemistry and Chemical Engineering , iCHEM , State Key Laboratory of Physical Chemistry of Solid Surface , Xiamen University , Xiamen 361005 , PR China.


We report here a novel Ti3-BPDC metal-organic framework (MOF) constructed from biphenyl-4,4'-dicarboxylate (BPDC) linkers and Ti3(OH)2 secondary building units (SBUs) with permanent porosity and large 1D channels. Ti-OH groups from neighboring SBUs point toward each other with an O-O distance of 2 Å, and upon deprotonation, act as the first bidentate SBU-based ligands to support CoII-hydride species for effective cascade reduction of N-heteroarenes (such as pyridines and quinolines) via sequential dearomative hydroboration and hydrogenation, affording piperidine and 1,2,3,4-tetrahydroquinoline derivatives with excellent activity (turnover number ∼ 1980) and chemoselectivity.

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