Diverse synthesis of C2-linked functionalized molecules via molecular glue strategy with acetylene

Although acetylene is an ideal two-carbon building block, very few catalytic methods can be applied to incorporate acetylene into fine chemicals. Here, the authors show photoredox-catalyzed syntheses of C2- linked molecules with gaseous acetylene under mild conditions. As the simplest alkyne and an abundant chemical feedstock, acetylene is an ideal two-carbon building block. However, in contrast to substituted alkynes, catalytic methods to incorporate acetylene into fine chemicals are quite limited. Herein, we developed a photoredox-catalyzed synthetic protocol for diverse C2-linked molecules via a molecular glue strategy using gaseous acetylene under mild conditions. Initiated by addition of an acyl radical to acetylene, two cascade transformations follow. One involves a double addition for the formation of 1,4-diketones and the other where the intermediate vinyl ketone is intercepted by a radical formed from a heterocycle. In addition to making two new C-C bonds, two C-H bonds are also created in two mechanistically distinct ways: one via a C-H abstraction and the other via protonation. This system offers a reliable and safe way to incorporate gaseous acetylene into fine chemicals and expands the utility of acetylene in organic synthesis.

Automated summary

In this study, the authors demonstrated a photoredox-catalyzed synthesis of C2-linked molecules using gaseous acetylene under mild conditions. The strategy not only enables the formation of two new C-C bonds, but also creates two C-H bonds in mechanistically distinct ways, offering a reliable and safe approach for incorporating acetylene into fine chemicals.