The Synthesis Of Cyclic Compounds And Malonates Based On The Functionalization Of Alkynes

Functionalization of alkynes have expanded significantly in the synthesis of organic chemicals. This principle is manifested in the conversion of petrochemical alkyne feedstocks into biologically active compounds through constructing new carbon-carbon bond or carbon-heteroatom bond. In this regard, the previous methods played an important role in the synthesis of pharmaceutical chemistry products.Spiro[4,5]trienones, 1-indanones, malonates and compounds containing C-S bond are important building blocks with wide applications in synthesis, as well as are importantly cores in many natural products, pharmaceutical molecules. The fast, simple, and efficient methods for their preparation are vital.This dissertation focuse on the synthesis of Spiro[4,5]trienones, 1-Indanones, Malonates and Compounds containing C-S bond. The content of dissertation includes five parts:1. Recent progress in the synthesis of cyclics and malonates has been described in detail. Three parts on the construction of chemicals are discussed in this chapter, including:(i) Advances in the construction of nitrogen-containing heterocyclic compound through the functionalization of alkynes,(ii) advances in the construction of carbocyclic compound through the functionalization of alkynes,(iii) advances in the construction of carbonyl complexes.2. An efficient copper-catalyzed oxidative ipso-cyclization of N-(p-Methoxyaryl)propiolamides with disulfides and H2 O Leading to 3-arylthio spiro[4,5]trienones, which plays an important role in the synthesis of products containing C-S and C-Se bond as a simple, good selectivity and inexpensive route.3. A new method for synthesis of functionalized 1-indanones through base-mediated cascade cyclization of o-alkynylbenzaldehydes with acetonitrile. This novel and inexpensive tandem route allows some new bonds, including a C-O bond and two C-C bonds, constructing 1-indanone in one step.4. A new metal-free method for the synthesis of malonates by DABCO-mediated tandem reaction of 3-halopropiolates at room temperature. This metal-free method which allows selective functionalization of the C-C triple bond is simple and highly general for selective synthesis of various unsymmetrical malonates with excellent functional group tolerance and good levels of selectivity control, and represents a mild and practical way to access 1,3-dicarbonyl compounds.5. A novel room temperature route to the C(sp3)-O bonds via metal-free Ph I(OAc)2-mediated oxygenation of benzylic C(sp3)-H bonds with N-hydroxyamides, in which a N-polyfluoroaryl amide group is used to activate the C(sp3)-H functionalization. This reaction enables a broad scope of benzamides and 2-arylacetamides to perform the benzylic C-H oxygenation. Importantly, its products can be utilized for heterocycles construction.