The present short review article highlights recent progress in the field of transition-metal catalysis. An overview on recent work involving cobalt-catalyzed cross-coupling reactions and some recent advances from our laboratories are given.1 Introduction2 Csp2–Csp2 Cobalt-Catalyzed Cross-Couplings3 Csp2–Csp3 Cobalt-Catalyzed Cross-Couplings4 Conclusion

Various 1,2-, 1,3-, and 1,4-substituted cyclic iodides or bromides undergo highly diastereoselective cross-couplings (diastereoselectivity (dr) up to 99:1) with a range of alkynylzinc pivalates, using CoCl (20 mol %) and trans- N, N, N', N'-tetramethylcyclohexane-1,2-diamine as a catalytic system.

A catalytic system consisting of CoCl·2LiCl and TMEDA enables the cross-coupling of various electron-poor aryl and heteroaryl halides with various alkynylzinc pivalates. Coupling with alkenyl halides proceeds with retention of configuration.

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