Photoredox/nickel cooperatively catalyzed radical allylic silylation of allyl acetates – Scope and mechanism

Metal-free photocatalyzed allylic silylation of allyl acetates and chlorides

“…19 Continuing our research on the synthesis and reactions of organosilicon compounds, 20 we present a novel metal-free photocatalyzed allylic silylation between silacarboxylic acids and readily available allyl acetates and chlorides. 21 This environmentally benign methodology enables the synthesis of a diverse range of allylsilanes in a highly stereoselective manner (Scheme 1c). The protocol demonstrated several key features: it is mild, robust, metal-free, highly stereoselective, and importantly, capable of tolerating both electron-withdrawing and -donating functional groups.…”

Decarboxylative Allylation of Silanecarboxylic Acids Enabled by Organophotocatalysis

“…15 Very recently, our group presented a photoredox and nickel dually catalyzed radical allylic silylation of allyl acetates. 16 Nevertheless, limitations exist with the above-mentioned strategies, in which undesired byproducts and metal salt wastes are unavoidably produced under transition metal catalysis. Therefore, the development of new methodologies for the installation of allylsilanes under transition-metal-free conditions remains highly attractive.…”

“…The combination of photocatalysis, HAT catalysis, and cobalt catalysis to effectuate allylic silylation of terminal alkenes was disclosed by Xu and co-workers (Scheme d) . Very recently, our group presented a photoredox and nickel dually catalyzed radical allylic silylation of allyl acetates . Nevertheless, limitations exist with the above-mentioned strategies, in which undesired byproducts and metal salt wastes are unavoidably produced under transition metal catalysis.…”

“…Inspired by this, we design an environmentally friendly organophotocatalyzed allylation of silanecarboxylic acids with allylic sulfones, affording various substituted allylsilanes (Scheme e). Up to now, such reactivity is particularly synthetically useful but scarce, not only because the products are wide-ranging in pharmaceutical and bioactive molecules but also because this allylic silylation proceeds under transition-metal-free conditions, in sharp contrast to the previous works. − …”