Although the advances on carbon halide reductive elimination have been made, the alkyl bromide and chloride analogues remain a challenge. Here, a palladium(0)-catalyzed iminohalogenation of γ,δ-unsaturated oxime esters is described, and the use of electron-poor phosphine ligands proved to be crucial to promoting alkyl bromide and chloride reductive elimination. Furthermore, S(N)2-type alkyl bromide and chloride reductive elimination has also been established.

Here, the highly enantioselective construction of 3,3-disubstituted tetrahydropyridines via Pd(0)-catalyzed asymmetric vinylborylation of (Z)-1-iodo-dienes and Bpin in the presence of a (S)-p-CF-BnPHOX ligand is reported. This process is supposed to be initiated by oxidative addition of Pd(0) to vinyl iodide, followed by transmetallation with Bpin, insertion of the pendant alkene and reductive elimination of alkyl-Pd(ii)-Bpin.

A general iron-catalyzed strategy for the atom-transfer radical cyclization (ATRC) of allylic halide is reported. Critical to this strategy is the use of DPPF [1,1'-bis(diphenylphosphino)ferrocene] as catalyst, which allows for efficient generation of the allylic radical species via a single-electron transfer (SET) process. The feasibility of achieving ATRC reactions of propargyl chlorides is also demonstrated, which affords products with an exocyclic allene moiety.

A Pd(0)/(S)-p-MeO-BnPHOX catalytic system has been established for the asymmetric reductive Heck reaction of (Z)-1-iodo-1,6-dienes, which affords quaternary tetrahydropyridines with good to excellent enantioselectivities. This reaction tolerates a wide range of substituted alkene moieties, including 1,1-disubstituted, 1,1,2-trisubstituted as well as 1,2-disubstituted alkenes.

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