Laboratory of Catalysis and Organic Synthesis, EPFL SB ISIC LCSO, BCH 4306, Ecole Polytechnique Fédérale de Lausanne, 1015, Lausanne, Switzerland.
Chemistry. 2019 Feb 26;25(12):3010-3013. doi: 10.1002/chem.201900020. Epub 2019 Jan 29.
1,2-Amino alcohols and α-aminocarbonyls are frequently found in natural products, drugs, chiral auxiliaries, and catalysts. This work reports a new method for the palladium-catalyzed oxyalkynylation and oxyarylation of propargylic amines. The reaction is perfectly regioselective based on the in situ introduction of a hemiacetal tether derived from trifluoroacetaldehyde. cis-Selective carbo-oxygenation was achieved for terminal alkynes, whereas internal alkynes gave trans-carbo-oxygenation products. The obtained enol ethers could be easily transformed into 1,2-amino alcohols or α-amino ketones using hydrogenation or hydrolysis, respectively.
1,2-氨基醇和α-氨基甲酰基经常存在于天然产物、药物、手性助剂和催化剂中。本工作报道了一种钯催化炔丙基胺的氧炔基化和氧芳基化的新方法。该反应具有完美的区域选择性，基于三氟乙醛原位引入的半缩醛连接基团。末端炔烃发生顺式选择性的碳氧键合，而内部炔烃则得到反式碳氧键合产物。得到的烯醇醚可以分别通过氢化或水解很容易转化为 1,2-氨基醇或α-氨基酮。
