Study On The Radical Reactions Promoted By Bu₃SnH/AIBN And Mn(OAc)₃

Over the past several decades, radical chemistry has advanced tremendously not only in principles but also in synthetic applications. Especially, radical reaction has been becoming more and more important recently. Owing to radical reaction possesses moderate condition, good regioselectivity and steroselectivity under some conditions, and it is becoming a very important tool in organic synthesis, and attracted considerable attention in the academia.The chapter 1 introduces the background and the applications of the free radical reactions promoted by Bu₃SnH/AIBN and Mn(OAc)₃.The chapter 2 concentrates on the free radical ring expansion of 1,3-diketones promoted by Bu₃SnH/AIBN. In addition, the corresponding cyclizations are also involved.The chapter 3 focuses on the reactions ofα-iodoketones and alkenes promoted by Mn(OAc)₃. The results show that the electron-deficientα,β-unsaturated esters yielded the cyclopropane derivatives, while electron-rich alkenes afforded iodine atom transfer products.The chapter 4 centers on Mn(OAc)₃-mediated regioselective phosphonation of arenes. The results show that both electron-donating and -withdrawing groups are all suitable for this reaction, the phosphonation occurs at ortho- or para- position of substituents in good yields. For diphenylphosphine oxide, the similar results were obtained.In chapter 5, we describe a simple, convenient and efficient protocol for the preparation of furan derivatives from the radical addition of 1,3-diketones to enol phosphates in the presence of Mn(OAc)₃. The different enol phosphates gave the similar yield of products, however, the yields greatly depended on the structure of the 1,3-diketones, 5,5-dimethylcyclohexane-1,3-dione afforded the best yield, while the cyclopentane-1,3-dione and pentane-2,4-dione produced the corresponding products in moderate yields.