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BPh3 and PhSiH3, represented as the stars Hikoboshi and Orihime, constitute a powerful catalytic system for deoxygenative CO2 conversions. According to a Japanese legend, this couple were banished to opposite sides of the Milky Way only coming together once a year. When BPh3 and PhSiH3 come together as catalyst and reductant, N‐methylaniline undergoes N‐methylation at room temperature under CO2 and...
BPh3 catalyzes the N‐methylation of secondary amines and the C‐methylenation (methylene‐bridge formation between aromatic rings) of N,N‐dimethylanilines or 1‐methylindoles in the presence of CO2 and PhSiH3; these reactions proceed at 30–40 °C under solvent‐free conditions. In contrast, B(C6F5)3 shows little or no activity. 11B NMR spectra suggested the generation of [HBPh3]−. The detailed mechanism...
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