Cascade Detrifluoroacetylation, C-S Bond Cleavage, and SN2' Reaction of α,α-Difluorinated Gem-Diols with MBH Esters

Xinyu Yao; Ziyi Li; Haibo Mei; Jorge Escorihuela; Vadim A Soloshonok; Jianlin Han

doi:10.1021/acs.joc.3c01220

Cascade Detrifluoroacetylation, C-S Bond Cleavage, and S_N2' Reaction of α,α-Difluorinated Gem-Diols with MBH Esters

J Org Chem. 2023 Sep 15;88(18):13057-13066. doi: 10.1021/acs.joc.3c01220. Epub 2023 Aug 30.

Authors

Xinyu Yao¹, Ziyi Li¹, Haibo Mei¹, Jorge Escorihuela², Vadim A Soloshonok^{3

4}, Jianlin Han¹

Affiliations

¹ Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China.
² Departamento de Química Orgánica, Universitat de València, Avda. Vicente Andrés Estellés s/n, Burjassot, Valencia 46100, Spain.
³ Department of Organic Chemistry I, Faculty of Chemistry, University of the Basque Country UPV/EHU, Paseo Manuel Lardizábal 3, San Sebastián 20018, Spain.
⁴ IKERBASQUE, Basque Foundation for Science, Alameda Urquijo 36-5, Plaza Bizkaia, Bilbao 48011, Spain.

PMID: 37647282
DOI: 10.1021/acs.joc.3c01220

Abstract

A new S_N2' reaction type of Morita-Baylis-Hillman (MBH) ester with sulfonyl anion, generated in situ via detrifluoroacetylation as a nucleophile is developed. Experimental results and DFT calculations disclose that the reaction proceeds via C-C bond cleavage to generate a PhSO₂CF₂ anion, C-S bond cleavage to generate a sulfonyl anion with the release of CF₂ carbene, and an S_N2' reaction with the MBH ester. The reaction features operational simplicity, wide substrate scope, high yields, and excellent stereoselectivity, which represents a new reaction mode of fluorinated gem-diols and also provides an efficient way to obtain β,γ-unsaturated sulfones.