Study On The Synthesis Of Oxindoles And Indoles Of Pharmaceutical Interest By Using Palladation Of Alkynes

The oxindoles and indole skelectons extensively distributed in a variety of compounds of biological, pharmaceutical and material interest. For example, these compounds are found to be prevalent for kinase inhibitory activities, which are promising to find lead compounds of anticancer drugs. Owing to greatly biological and pharmaceutical potentialities, considerable efforts have been devoted to the construction of these oxindole and indole skelectons.This dissertion mainly describes several effective methods for the synthesis of oxindole and indoles, such as 3-(acetoxylmethylene) oxindoles, 3-(aminomethylene) oxindoles, 3-(diarylmethylene)oxindoles and 3-haloindoles, via the palladation of alkynes.The first part of this dissertion reports a procedure for the utilization of various palladation of alkyne in organic synthesis. So far, all of halopalladtion, aminopalladation, acetoxylpalladation, etc have successfully been used in the organic synthesis, which provides a lot of acesses to a variety of compounds of biologieal, pharmaceutical and material interestThe second part describes a palladium-catalyzed intermolecular aminopalladation /C-H activation method for selectively synthesizing (E)-(2-oxindolin-3-ylidene) -phthalimides. In the presence of Pd(OAc)2 and PhI(OAc)2, alkynes were ifunctionalized with a phthalimide and an arene sp2 C-H bond to selectively synthesize (E)-(2-oxoindolin-3-ylidene) phthalimides, which products are of great potential pharmaceutical valueproducts in many major therapeutic areas, such as oncology, inflammation, neurology, immunology, and endocrinology. To the best of our knowledge, the reaction serves as the first example of intermolecular aminopalladation/C-H activation reactions of alkynes.The third part desribes a palladium-catalyzed oxidative C-H functionalization protocol for the synthesis of (2-oxoindolin-3-ylidene)methyl acetates. In the presence of Pd(OAc)2, and PhI(OAc)2, a variety of N-arylpropiolamides underwent the C-H functionalization reaction with acids to selectively afford the corresponding (E)-(2-oxoindolin-3-ylidene)methyl acetates in moderate to excellent yields.The fourth part describes a selective palladium-catalyzed carbonylative annulation process for the synthesis of 3-(halomethylene)indolin-2-ones. In the presence of PdX2 and CuX2, 3-(halomethylene)indolin-2-ones were selectively obtained from the carbonylative annulations of 2-(1-alknyl)benzenamines with CO in moderate to good yields.The fifth part describes an effective protocol for the synthesis of 3-halo-2-substituted-1H-indoles by PdX2/CuX2-catalyzed annulations of 2-ethynylbenzenamines. In the presence of PdX2 and CuX2, the annulation reactions of a variety of 2-ethynylbenzenamines were conducted in moderate to good yields. It is noteworthy that only N-acetyl protected 2-ethynylbenzenamines can undergo the reaction successfully.The sixth part describes a selective and efficient method for the synthesis of 3-(1-arylmethylene)oxindoles by palladium-catalyzed C-H functionalization of anilides with aryliodonium salts. In the presence of Pd(OAc)2 and Et3N, a variety of anilides underwent the reaction with aryliodonium salts to afford the corresponding 3-(1-arylmethylene)oxindoles in moderate to good yields. It is noteworthy that the reaction can be conducted providing moderate yields even without bases.