Sila-spirocyclization involving unstrained C(sp<sup>3</sup>)-Si bond cleavage.

Shi, Yufeng; Shi, Xiaonan; Zhang, Jinyu; Qin, Ying; Li, Bo; Zhao, Dongbing · Nat Commun · 2022

basic_science · Level V

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Abstract

C - Si Bond cleavage is one of the key elemental steps for a wide variety of silicon-based transformations. However, the cleavage of unstrained Si-C(sp3) bonds catalyzed by transition metal are still in their infancy. They generally involve the insertion of a M - C(sp2) species into the C - Si bond and consequent intramolecular C(sp2)‒Si coupling to exclusively produce siloles. Here we report the Pd-catalyzed sila-spirocyclization, in which the Si-C(sp3) bond is activated by the insertion of a M - C(sp3) species and followed by the formation of a new C(sp3)‒Si bond, allowing the construction of diverse spirosilacycles. This reactivity mode, which is strongly supported by DFT calculations may open an avenue for the Si-C(sp3) bond cleavage and silacycle synthesis.