Parts of the mechanistic studies, detailed experimental procedures, characterization data, and copies of 1 H and 13 C NMR spectra for new compounds (PDF)

Catalytic alkylation of stable alkenyl C−O electrophiles is synthetically appealing, but studies to date have typically focused on the reactions with alkyl Grignard reagents. We report herein a cross‐electrophile reaction of alkenyl acetates with alkyl bromides. This work has enabled a new method for the synthesis of aliphatic alkenes from alkenyl acetates to be established that can be used to add more structural complexity and molecular diversity with enhanced functionality tolerance. The method allows for a gram‐scale reaction and modification of biologically active molecules, and it affords access to useful building blocks. Preliminary mechanistic studies reveal that the NiI species plays an essential role for the success of the coupling of these two reactivity‐mismatched electrophiles.

The construction of a C–C bond is a center subject in synthetic organic chemistry. The cross-electrophile coupling has provided a powerful tool to forge the C–C bond. However, this process generally requires organic halides, which has severely restricted the design space for new reactions. Herein, we highlight our recent work on the coupling reaction between C–N and C–O electrophiles. This work demonstrates the possibility of construction of C–C bond via C–N and C–O cleavage. A number of reactions between benzyl ammoniums and vinyl acetates, aryl ammoniums and vinyl acetates, and benzyl ammoniums and aryl C–O electrophiles have been studied. We also disclosed that benzyl ammonium salts can be activated by low-valent nickel to be radicals.1 Introduction2 Cross-Coupling of C–N and C–O Electrophiles3 Summary and Outlook

Catalytic alkylation of stable alkenyl C−O electrophiles is synthetically appealing, but studies to date have typically focused on the reactions with alkyl Grignard reagents. We report herein a cross‐electrophile reaction of alkenyl acetates with alkyl bromides. This work has enabled a new method for the synthesis of aliphatic alkenes from alkenyl acetates to be established that can be used to add more structural complexity and molecular diversity with enhanced functionality tolerance. The method allows for a gram‐scale reaction and modification of biologically active molecules, and it affords access to useful building blocks. Preliminary mechanistic studies reveal that the NiI species plays an essential role for the success of the coupling of these two reactivity‐mismatched electrophiles.