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

• Published in: Nature communications 2022-04, Vol.13 (1), p.1858-1858, Article 1858
• Main Authors: Yang, Bo, Lu, Shaodong, Wang, Yongdong, Zhu, Shifa
• Format: Article
• Language: English
• Subjects: 639/638/403/933; 639/638/77/890; 96/98; Acetylene; Acids; Alkynes; Carbon; Chemical synthesis; Chemicals; Diketones; Fine chemicals; Humanities and Social Sciences; Hydrogen; Ketones; Laboratories; multidisciplinary; Photoredox catalysis; Protonation; Radicals; Raw materials; Reagents; Science; Science (multidisciplinary)
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-022-29556-2

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. 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.