Department of Chemistry Seminar - Silicon Effect-Directed Synthesis of Organofluorine Compounds

Speaker: Professor Xiao SHEN

Institution: The Institute for Advanced Studies, Wuhan University, Wuhan, China

Hosted By: Professor Yangjian QUAN

Abstract

Organofluorine molecules play an indispensable role in life sciences and materials science. However, organic fluorine compounds are extremely rare in nature, where fluorine primarily exists in inorganic forms such as fluorite. The vast majority of organic fluorine compounds must be synthetically produced. Consequently, the development of novel fluorination reagents and reactions has long been a frontier research direction in synthetic chemistry. The construction of innovative fluorine-containing molecular architectures can provide new strategies for drug chemists and materials scientists in functional molecule design, while advances in fluorination methodologies may offer pathways to circumvent existing synthetic patents for pharmaceutical molecules.

In exploring strategies for the precise synthesis of organofluorine compounds, we observed a previously overlooked silicon effect in synthetic chemistry: the ability of a silyl group to stabilize α- and β-carbon radicals. Although this "silicon effect" has been documented in the literature (1), its potential in synthetic chemistry remains significantly underexplored. This presentation will introduce a series of new reactions developed by our group utilizing the "silicon-stabilization of adjacent radicals" strategy, enabling controlled generation and transformation of monoradicals, diradicals, carbenes, and ketenes, along with their applications in the precise synthesis of organofluorine compounds (2).

Keywords: fluoroalkylation, silicon effect, radical, carbene, ketene, photocatalysis

Reference:

1. Davidson, I. M. T.; Barton, T. J.; Hughes, K, J.; Ijadi-Maghsoodi, S.;  Revis, A.; Paul, G. C. Organometallics 1987, 6, 644.

2.  (a) Shen, X. Acc. Chem. Res. 2025, 58, 1519-1533. (b) Zhang, Y.; Zhou, G.; Liu, S.; Shen, X. Chem. Soc. Rev. 2025, 54, 1870-1904. (c) He, X.; Zhang, Y.; Liu, S.; Zhang, W.; Liu, Z.; Zhao, Y.; Shen, X. Nat. Synth. 2025, 4, 188. (d) Zhou, G.; Li, Y.;  Liu, Y.; He, X.; Liu, S.; Shen, X. J. Am. Chem. Soc. 2025, 147, 15955. (e) Niu, Y.; Jin, C.; He, X.; Deng, S.; Zhou, G.; Liu, S.; Shen, X. Angew. Chem. Int. Ed. 2025, e202507789.  (f) Zhou, G.; Yao, Y.; He, X.; Zhang, W.; Liu, S. Shen, X. Chem 2025,102721. (g) Zhou, G.; Guo, Z.; Liu, S.; Shen, X. J. Am. Chem. Soc. 2024, 146, 4026-4035. (h) Li, Z.; Zhang, Z.; Zhang, Z.; Shen, X. Sci. China Chem. 2024, 67, 3662-3668. (i) Li, Z.; Zhang, Y.; Zhang, Y.; He, X. Shen, X. Angew. Chem. Int. Ed. 2023, 62, e202303218. (j) Zhang, Y.; Zhou, G.; Gong, X.; Guo, Z.; Qi, X.; Shen, X. Angew. Chem., Int. Ed. 2022, 61, e202212201. (k) Zhou, G.; Shen, X. Angew. Chem. Int. Ed. 2022, 61, e202115334. (l) Zhang, Y.; Niu, Y.; Guo, Y.; Wang, J.;  Zhang, Y.; Liu, S.; Shen, X. Angew. Chem. Int. Ed. 2022, 61, e202212201.