A nickel-catalyzed direct reductive cross-coupling of disubstituted cycloalkyl iodides with aryl iodides was developed. The one-pot reaction, which is simple to operate, was capable of proceeding efficiently in a stereocontrolled manner to afford a variety of cross-coupled products with high diastereoselectivity and wide functional group tolerance.

An efficient indium-mediated difunctionalization of iodoalkyl-tethered unactivated alkenes via cyclization/cross-coupling sequence was developed. The reactions proceeded effectively with wide functional group tolerance, leading to a wide variety of cyclic compounds,...

Lead was found to efficiently mediate the allylation reactions of carbonyl compounds with cyclic allylic halides in the presence of stoichiometric amounts of lithium chloride and a catalytic amount of GaCl3 (20 mol %), leading to the desired homoallylic alcohols in modest to high yields with excellent diastereocontrol (>99:1 syn/anti) and good functional group tolerance. In contrast, the use of either 2-pyridinecarboxaldehyde as the carbonyl substrate or (E)-cinnamyl bromide as the allylating agent produced the corresponding product with reversed diastereoselectivity (>99:1 anti/syn).

The reaction of non‐fluorinated silyl enol ether with alkyne is useful for the synthesis of β,γ‐unsaturated carbonyl compounds. However, most of the existing methods for realizing such organic transformation usually employ stoichiometric amounts of relatively expensive Lewis acids/metallic salts. Herein, an iron(III)‐catalyzed difluoroalkylation of aryl alkynes with difluoroenol silyl ether was developed. The reactions proceeded smoothly in the presence of a catalytic amount of iron(III) chloride, stoichiometric amounts of trimethylsilyl chloride, and 4 Å molecular sieves in dichloroethane (DCE) to afford the corresponding α‐alkenyl‐α,α‐difluoroketones in modest to good yields. Remarkably, among the various metallic salts screened, cheap and less‐toxic iron(III) salt was found to be the most efficient Lewis acid catalyst for the present reaction. In addition, in the absence of iron(III) chloride or trimethylsilyl chloride, either no reaction occurred or considerably reduced reaction performance was observed. Moreover, the use of Brønsted acid to replace iron(III) chloride as reaction catalyst failed to promote the reaction. The reaction could be scaled up and the obtained difluoroalkylated carbonyl compound serves as a versatile building block which could be subjected to late‐stage diversification to be converted into useful organic molecules containing CF2H and CF2CF2 moieties. Deuterated experiments showed that the proton in the generated alkene product should originate from trace amounts of water present in the reaction system.