Iron-Catalyzed Tertiary Alkylation of Terminal Alkynes with1,3-Diesters via a Functionalized Alkyl Radical

Ming-Qing Tian,^a,+Zhen-Yao Shen,^a,+Xuefei Zhao,^aPatrick J. Walsh,^b,* and Xu-Hong Hu^a,*

^aInstitute of Advanced Synthesis,School of Chemistry and Molecular Engineering,Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816 (China)

^bRoy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, PA 19104 (USA)

⁺These authors contributed equally.

Abstract:Direct oxidative C(sp)-H/C(sp³)-H cross-couplingoffers an ideal and environmentally benign protocol forC(sp)-C(sp³) bond formations. As such, reactivity and site-selectivitywith respect to C(sp³)-H bond cleavage haveremained a persistent challenge. Herein is reported a simple method for iron-catalyzed/silver-mediated tertiary alkylationof terminal alkynes with readily available and versatile 1,3-dicarbonyl compounds. The reaction is suitable for an array of substrates and proceeds in a highly selective manner evenemploying alkanes containing other tertiary, benzylic, and C(sp³)-H bonds alpha to heteroatoms. Elaboration of theproducts enables the synthesis of a series of versatile buildingblocks. Control experiments implicate the in situ generation ofa tertiary carbon-centered radical species.

Angew. Chem. Int. Ed.,Doi: 10.1002/anie.202100641 (2019年影响因子：12.959)

论文链接：https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.202100641