Title: Reversal of Regioselectivity in Ynamide Chemistry

Authors: Bo Zhou,Tong-De Tan,Xin-Qi Zhu,Mingzhou Shang,Long-Wu Ye

Abstract:

Ynamides are special alkynes bearing an electron-withdrawing group on the nitrogen atom, and have been extensively studied over the past decade. However, the addition of functional groups across ynamides in these transformations typically occurs at the α-position of ynamides due to the strong polarization of the alkynyl moiety. Studies on the umpolung transformations in ynamide chemistry may not only discover organic reactions, but also lead to the divergent organic synthesis, thus significantly enriching the ynamide chemistry. This review summarizes four main strategies utilized to achieve the reversal of regioselectivity, including ring strain factor, metal−carbonyl (or sulfonyl) chelation, base-mediated and radical-initiated addition.

Full-Link:https://pubs.acs.org/doi/10.1021/acscatal.9b01851