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Cross-electrophile coupling has emerged as a promising tool for molecular synthesis; however, current studies have focused mainly on forging CÀC bonds. We report a crosselectrophile CÀGe coupling reaction and thereby demonstrate the possibility of constructing organogermanes from carbon electrophiles and chlorogermanes. The reaction proceeds under mild conditions and offers access to both aryl and alkenyl germanes. Electron-rich, electron-poor, and ortho-/ meta-/para-substituted (hetero)aryl electrophiles, as well as cyclic and acyclic alkenyl electrophiles, were coupled. Gramscale reaction, incorporation of the -GeR 3 moiety into complex biologically active molecules, and derivatization of formed organogermanes are demonstrated.

Catalytic asymmetric dicarbofunctionalization of tethered alkenes has emerged as a promising tool for producing chiral cyclic molecules; however, it typically relies on aryl-tethered alkenes to form benzene-fused compounds. Herein, we report an enantioselective cross-electrophile divinylation reaction of nonaromatic substrates, 2-bromo-1,6-dienes. The approach thus offers a route to new chiral cyclic architectures, which are key structural motifs found in various biologically active compounds. The reaction proceeds under mild conditions, and the use of chiral t-Bu-pmrox and 3,5-difluoro-pyrox ligands resulted in the formation of divinylated products with high chemo-, regio-, and enantioselectivity. The method is applicable for the incorporation of chiral hetero-and carbocycles into complex molecules.

The synthesis of alkenes (olefins) is a central subject in the synthetic community. The transition-metal-catalyzed reductive cross-coupling of vinyl electrophiles has emerged as a promising tool to produce alkenes with improved flexibility, structural complexity, and functionality tolerance. In this review, we summarized the progress in this field with respect to cross-electrophile couplings and reductive Heck reactions using vinyl electrophiles.1 Introduction2 Cross-Electrophile Coupling of Vinyl Electrophiles3 Reductive Heck Reaction of Vinyl Electrophiles4 Summary and Outlook

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