Iron-Catalyzed Tertiary Alkylation of Terminal Alkynes with 1,3-Diesters via a Functionalized Alkyl Radical

Ming-Qing Tian,^a,+ Zhen-Yao Shen,^a,+ Xuefei Zhao,^a Patrick 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-coupling offers an ideal and environmentally benign protocol for C(sp)-C(sp³) bond formations. As such, reactivity and site-selectivity with respect to C(sp³)-H bond cleavage have remained a persistent challenge. Herein is reported a simple method for iron-catalyzed/silver-mediated tertiary alkylation of 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 even employing alkanes containing other tertiary, benzylic, and C(sp³)-H bonds alpha to heteroatoms. Elaboration of the products enables the synthesis of a series of versatile building blocks. Control experiments implicate the in situ generation of a 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