High Chemo-/Stereoselectivity for Synthesis of Polysubstituted Monofluorinated Pyrimidyl Enol Ether Derivatives

• DOI: 10.1021/acs.orglett.1c00092
• Publication Date: 2021-02-19T07:57:36Z
• Authors: Lei Kang; Fang Wang; Jinlong Zhang; Huameng Yang; Chungu Xia; Jinlong Qian; Gaoxi Jiang
• Keywords: Polysubstituted Monofluorinated Pyr.; carbon nucleophile; Ecology; carbon nucleophilic addition reacti.; α- fluoro -β-keto; novel intramolecular Smiles rearran.; Biochemistry; 01 natural sciences; 0104 chemical sciences; pyrimidine 2- carbon; Sociology; enol oxyanion; Medicine; fine-tuning reaction conditions

A novel intramolecular Smiles rearrangement of α-fluoro-β-keto-pyrimidylsulfones (usually used as a carbon nucleophile) was developed, providing a versatile avenue for synthesis of tri/tetra-substituted monofluorinated pyrimidyl enol ethers. Among these, diverse (Z)-monofluorovinylsulfones and sulfinates were efficiently assembled by adding extra electrophile and fine-tuning reaction conditions. The process is triggered by a keto-enol tautomerism from enol oxyanion to pyrimidine 2-carbon, completely different from the classical carbon nucleophilic addition reaction approach.