Iridium-Catalyzed [2+2+2] Cycloaddition of alpha,omega-Diynes with Cyanamides

作者：Hashimoto Toru; Ishii Satoshi; Yano Reiko; Miura Hiroki; Sakata Ken; Takeuchi Ryo^*

来源：Advanced Synthesis & Catalysis, 2015, 357(18): 3901-3916.

DOI：10.1002/adsc.201500637

• 2-aminopyridines
• cyanamides
• cycloaddition
• diynes
• iridium

The complex [Ir(cod)Cl](2)/DPPF or racBINAP is an efficient catalyst for the [2+2+2] cycloaddition of alpha,omega-diynes with cyanamides. A wide range of cyanamides derived from secondary amines are good coupling partners for alpha,omega-diynes. The reaction of unsymmetrical alpha,omega-diynes possessing two different internal alkyne moieties with cyanamides is regioselective. A competitive experiment showed that cyanamide is more reactive than nitrile. This higher reactivity of cyanamide than nitrile was analyzed based on density functional theory (DFT) calculations at the B3LYP level.

• 出版日期2015-12-14