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

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

doi:10.1038/s41467-022-34466-4

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

Nat Commun. 2022 Nov 5;13(1):6697. doi: 10.1038/s41467-022-34466-4.

Authors

Yufeng Shi¹, Xiaonan Shi¹, Jinyu Zhang¹, Ying Qin¹, Bo Li², Dongbing Zhao³

Affiliations

¹ State Key Laboratory and Institute of Elemento-Organic Chemistry, Haihe Laboratory of Sustainable Chemical Transformations, College of Chemistry, Nankai University, Tianjin, 300071, China.
² Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, 91106, USA. bli3@caltech.edu.
³ State Key Laboratory and Institute of Elemento-Organic Chemistry, Haihe Laboratory of Sustainable Chemical Transformations, College of Chemistry, Nankai University, Tianjin, 300071, China. dongbing.chem@nankai.edu.cn.

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.