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Sila-spirocyclization involving unstrained C(sp3)−Si bond cleavage

Yufeng Shi, Xiaonan Shi, Jinyu Zhang, Ying Qin, Bo Li, Dongbing Zhao

2022Nature Communications24 citationsDOIOpen Access PDF

Abstract

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(sp 3 ) bonds catalyzed by transition metal are still in their infancy. They generally involve the insertion of a M − C(sp 2 ) species into the C − Si bond and consequent intramolecular C(sp 2 )‒Si coupling to exclusively produce siloles. Here we report the Pd-catalyzed sila-spirocyclization, in which the Si−C(sp 3 ) bond is activated by the insertion of a M − C(sp 3 ) species and followed by the formation of a new C(sp 3 )‒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(sp 3 ) bond cleavage and silacycle synthesis.

Topics & Concepts

Cleavage (geology)Intramolecular forceBond cleavageChemistryCatalysisStereochemistrySiliconCrystallographyMaterials scienceOrganic chemistryComposite materialFracture (geology)Organoboron and organosilicon chemistryCatalytic Cross-Coupling ReactionsCatalytic C–H Functionalization Methods
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