ABSTRACT
Site selective functionalization of inert remote C(sp3)-H bonds to increase molecular complexity offers vital potential for chemical synthesis and new drug development, thus it has been attracting ongoing research interest. In particular, typical ß-C(sp3)-H arylation methods using chelation-assisted metal catalysis or metal-catalyzed oxidative/photochemical in situ generated allyl C(sp3)-H bond processes have been well developed. However, radical-mediated direct ß-C(sp3)-H arylation of carbonyls remains elusive. Herein, we describe an iodoarene-directed photoredox ß-C(sp3)-H arylation of 1-(o-iodoaryl)alkan-1-ones with cyanoarenes via halogen atom transfer (XAT) and hydrogen atom transfer (HAT). The method involves diethylaminoethyl radical-mediated generation of an aryl radical intermediate via XAT, then directed 1,5-HAT to form the remote alkyl radical intermediate and radical-radical coupling with cyanoarenes, and is applicable to a broad scope of unactivated remote C(sp3)-H bonds like ß-C(sp3)-H bonds of o-iodoaryl-substituted alkanones and α-C(sp3)-H bonds of o-iodoarylamides. Experimental findings are supported by computational studies (DFT calculations), revealing that this method operates via a radical-relay stepwise mechanism involving multiple SET, XAT, 1,5-HAT and radical-radical coupling processes.
ABSTRACT
Articular cartilage injury is a prevalent clinical condition resulting from trauma, tumors, infection, osteoarthritis, and other factors. The intrinsic lack of blood vessels, nerves, and lymphatic vessels within cartilage tissue severely limits its self-regenerative capacity after injury. Current treatment options, such as conservative drug therapy and joint replacement, have inherent limitations. Achieving perfect regeneration and repair of articular cartilage remains an ongoing challenge in the field of regenerative medicine. Tissue engineering has emerged as a key focus in articular cartilage injury research, aiming to utilize cultured and expanded tissue cells combined with suitable scaffold materials to create viable, functional tissues. This review article encompasses the latest advancements in seed cells, scaffolds, and cytokines. Additionally, the role of stimulatory factors including cytokines and growth factors, genetic engineering techniques, biophysical stimulation, and bioreactor systems, as well as the role of scaffolding materials including natural scaffolds, synthetic scaffolds, and nanostructured scaffolds in the regeneration of cartilage tissues are discussed. Finally, we also outline the signaling pathways involved in cartilage regeneration. Our review provides valuable insights for scholars to address the complex problem of cartilage regeneration and repair.
