Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607-7061, USA.
J Am Chem Soc. 2013 Mar 27;135(12):4668-71. doi: 10.1021/ja400477r. Epub 2013 Mar 14.
Arynes generated directly from alkyne building blocks in the presence of silver catalysts effectively activate primary, secondary, and tertiary alkane C-H bonds. This C-H insertion requires only a catalytic amount of silver complex and modest heating compared to harsh conditions and extra promoters including directing groups, oxidants, and bases in typical transition-metal-based C-H bond functionalizations. Preliminary mechanistic studies suggest that the C-H bond-breaking and new bond-forming events take place in a concerted manner, rendering a formal 1,2-addition of C-H bond across the π-bond of arynes.
芳基炔烃可以在银催化剂的作用下直接从炔烃砌块中生成，从而有效地活化伯、仲、叔烷烃的 C-H 键。与典型的过渡金属催化的 C-H 键官能化反应所需的苛刻条件以及外加导向基团、氧化剂和碱相比，这种 C-H 插入仅需要催化量的银配合物和适度加热。初步的机理研究表明，C-H 键的断裂和新键的形成是协同进行的，使得芳基炔烃的π键上的 C-H 键以 1,2-加成的形式断裂。
