Hiyama's reactionHiyama's reaction (Hiyama's reaction) refers to the palladium-or nickel-catalyze cross-linking reaction between an aromatic, alcoholic, alkyi, or pseudo-halo (such as triflate) and an organic Silane. Similar to the Suzuki reaction, this reaction also required an activating agent, such as a fluoridation ion (TAFF, TBaF) or a base (such as NaOx, Na2CO3), to form an activated highly-coordinated silicon intermediate during the metal transfer. Otherwise, the reaction would be difficult to carry out. The Catalysis Cycle is similar to the Kumada Couplings. The substitution group on the silicon usually had to be a heteroatom or a aromatic group. If it was a trialkyi Silane, it would be difficult to form a Silicate intermediate, so the couple reaction was difficult to carry out.
This reaction had many advantages, including high atom economy, low environmental impact, easy storage of the organic silicon reagent, easy operation, low toxicity, mild reaction conditions, high yield and selectively, and good tolerance to other functional groups. However, the compatibility of the protective group with silicon, the difficulty of preparing the organic silicon, and the high cost of the activating agent limited the application of this reaction to a certain extent.
The reaction cycle went through several steps: the addition of oxygen, the metalization, the cis-transcrystallisation, and the reduction and elimination. The key was to activate the Si-R bond so that metal-metal exchange could take place. By adding an organic fluorin reagent, such as TBaF, through the reaction of F and Si, a +5-valency Si was formed, thereby activating the C-Si bond. However, the reaction rate can also be increased by using a Silane with an R''group, such as a Fluoro or an Alkyl group, instead of an Alkyl group.
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