Me3SiCl促进亚铁氰化钾为氰源的α,β-不饱和酮的共轭氢氰化有机化学.pdfVIP

DOI: 10.6023/cjoc201501019 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE Me SiCl 促进亚铁氰化钾为氰源的α,β-不饱和酮的共轭氢氰化 3 杨靖亚* 占宝华 马 奔 向现成 保云芬 李 政 (西北师范大学化学化工学院 兰州 730070) 摘要 发展了一种以无毒的亚铁氰化钾为环境友好氰源、Me3SiCl 促进的 α,β-不饱和酮的共轭氢氰化方法. 采用“一锅 法”, 中间体三甲基硅氰无需分离. 在 1 mol% Cs CO 催化下, 芳香类和脂肪类 α,β-不饱和酮专一区域选择性地转化为 2 3 相应的共轭氢氰化产物 β-氰基酮. 不使用传统的剧毒氰化试剂以及反应活性中间体三甲基硅氰无需分离等特点使得该 方法具有较好的应用前景. 关键词 Michael 加成; 氰化物; α,β-不饱和酮; 绿色化学; 亚铁氰化钾 Me SiCl-Promoted Conjugate Hydrocyanation of α,β-Unsaturated 3 Ketones Using Potassium Hexacyanoferrate(II) as Cyanide Source Yang, Jingya* Zhan, Baohua Ma, Ben Xiang, Xiancheng Bao, Yunfen Li, Zheng (College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070) Abstract A Me SiCl-promoted conjugate hydrocyanation of α,β-unsaturated ketones using non-toxic potassium hexacy- 3 anoferrate(II) as an eco-friendly cyanide source is described. By “one-pot” procedure, the intermediate, trimethylsilyl cyanide, does not need separation. With 1 mol% Cs CO as catalyst, a variety of aromatic and aliphatic α,β-unsaturated ketones afforded 2 3 the corresponding β-cyano ketones regioselectivity exclusively. Avoiding the traditional highly toxic cyanide and without sep- aration of the reactive intermediate trimethylsilyl cyanide make this protocol more practical. Keywords Michael addition; cyanides; α,β-unsaturated ketones; green chemistry; potassium hexac