Palladium‐Catalyzed Benzylic Silylation of Diarylmethyl Carbonates with Silylboranes under Base‐Free Conditions

Abstract

A palladium‐catalyzed benzylic silylation of diarylmethyl carbonates with silylboranes has been developed. The reaction proceeds smoothly even under external base‐free conditions, and the corresponding benzylic silanes are formed in good to high yields. The obtained benzyl silane derivatives can work as the benzylic nucleophiles by the action of a suitable fluoride source and react with some carbon electrophiles to deliver the corresponding benzylic C−C cross‐coupled products. Additionally, while still preliminary, the allylic silylation of the isoelectronic allylic carbonates is also achieved.

Pd/Ming-Phos-Catalyzed Asymmetric Three-Component Arylsilylation of N-Sulfonylhydrazones: Enantioselective Synthesis of gem-Diarylmethine Silanes

“…Nevertheless, most transformations are limited to arylalkylmethine silanes. The catalytic, efficient, and enantioselective assembly of chiral gem -diarylmethine silanes, those with two sterically similar aromatic substituents, poses considerable challenges, and only a handful of examples have been reported, though the diarylmethane skeleton is commonly found in many bioactive compounds . Among the strategies used, reactions through chirality transfer have been sporadically reported, including the palladium-catalyzed reaction of benzylic chloride with silyl boronate and the nickel-catalyzed reaction of benzylic methyl ether with silyl Grignard reagent (Scheme a), , both of which gave chiral gem -diarylmethine silanes with moderate enantiopurity.…”