Syntheses of Atypically Fluorinated Peptidyl Macrocycles through Sequential Vinylic Substitutions
作者:Tomoyuki Tsunemi、Salvador J. Bernardino、Angel Mendoza、Christopher G. Jones、Patrick G. Harran
DOI:10.1002/anie.201910136
日期:2020.1.7
Small peptides containing combinations of cysteine, tyrosine, histidine, and serine residues react with octafluorocyclopentene (OFCP) to afford atypically structured macrocycles through successive vinylic substitutions. The reactions proceed rapidly in air at 0 °C and are tolerant of spectating tryptophan, asparagine, glutamine, and threonine residues. Hexapeptides of consensus sequence YXCXXC displace
包含半胱氨酸,酪氨酸,组氨酸和丝氨酸残基组合的小肽与八氟环戊烯(OFCP)反应,通过连续的乙烯基取代提供非典型结构的大环。该反应在0°C的空气中迅速进行,可耐受色氨酸,天冬酰胺,谷氨酰胺和苏氨酸残基。共有序列YXCXXC的六肽取代了OFCP中的四个氟原子,生成了具有双转弯表面的氟化大双环化合物。该方法提供了对广泛的先前未知的杂环结构的便捷访问。