The Mizoroki‐Heck reaction is one of the most valuable reactions for functionalizing C−C double bonds in the presence of a Pd catalyst. This protocol is suitable for the reaction of a C(sp2)‐halide with a terminal olefin to produce a trans‐1,2‐disubstituted olefin. However, reports of the Mizoroki‐Heck reaction of internal olefins are rare and impractical due to the low reactivity of internal olefins and problems of product diastereoselectivity. In this review, we summarize Mizoroki‐Heck reactions of internal olefins with aryl or alkyl halides to illustrate their reactivities and stereoselectivities.

Herein, we report an efficient method for the stereoconvergent tertiary alkylations of (E)- and (Z)-mixed internal olefins (styrenes, enamides, and vinylic ethers) to produce trisubstituted olefins bearing a quaternary carbon center via an addition/elimination reaction in the presence of an iron catalyst. (E)- and (Z)-mixed internal olefins with various E/Z ratios reacted smoothly with α-bromocarbonyls as a tertiary alkyl source to exclusively produce (E)-trisubstituted olefins. Mechanistic studies revealed that each of the (E)- and (Z)-internal olefins exhibited the same reactivity, and the exclusive generation of (E)-trisubstituted olefin products could be attributed to the β-hydrogen elimination of an alkyl iron species. The developed method can be used to synthesize highly congested trisubstituted olefins containing a quaternary carbon atom that bears various alkyl chains.

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There are several reports of lactam cyclizations, but most yield less-substituted lactam rings. Therefore, diastereoselective cyclization to yield highly substituted lactams is one of the challenges in this field. We...

Herein, we report an efficient method using transition metal catalysts for controlling atom-transfer radical cyclization elimination (ATRCE) and atom-transfer radical cyclization (ATRC) in the reaction of α-bromocarbonyls possessing a styrene moiety. An iron salt efficiently catalyzed the ATRCE to produce cyclic compounds possessing a C-C double bond. On the other hand, the copper catalyst produced halogenated cyclic compounds.