Mechanistic study reveals cooperative palladium and Lewis acid catalysis for silicon-methyl bond activation, enabling the stepwise conversion of chlorotrimethylsilane into diverse silanols.
A novel mode of Si─Me bond activation has been unveiled through the cooperative action of a P‐directing group, a palladium catalyst and a Lewis acid. The pivotal role of the Lewis acid in enabling the activation of the strong and low‐polarity Si─Me bond was elucidated via stoichiometric experiments. According to DFT calculations, the Lewis acid acts as a Me − acceptor and triggers the formation of the key cationic silyl Pd complex responsible for the alkyl exchange at Si. This unprecedented Si─Me bond transformation has been demonstrated in a four‐step sequence, enabling the stepwise upgrading of Me 3 SiCl into silanols bearing diverse organic substituents.
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Kameo et al. (2026) studied this question.
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