Synthesis Of Polycyclic Compounds And Nitriles Based On Functionalized 1,6-enynes And 1,6-alkynones

Cyclic isomerization of alkynes is a kind of very important reaction,one of the most important advantages is that it can quickly synthesize complex ring compounds,so the study of cycloisomerization of alkynes has been one of the research hotspots in organic chemistry.Much progress has been made in this type of response over the past20 years.However,there are relatively few studies on cycloisomerization reactions of substrates containing three or more unsaturated elements.Therefore,it is of great value to use such alkynes to synthesize carbon ring skeletons with more complex structures,and its target products may be used in the synthesis of natural products.Nitrile compounds are common organic intermediates and chemical raw materials,which can be widely used in the synthesis of drug intermediates or other important chemicals.Therefore,the synthesis of nitrile compounds has important economic and academic value.In this paper,a method of synthesizing complex polycyclic compounds using alkynes and a method of synthesizing carbonyl nitriles using alkynyl ketones as raw materials were developed respectively according to the above research status.Topic 1:A method for synthesis of polycyclic compounds by using Pt Cl₂catalyzed intramolecular isomerization of N atom-bonded dienyne was developed.Under mild conditions,the selective formation of azabicyclic[4.1.0]heptenes and N-polycyclic systems containing dicyclopropyl condensation is guided by the linkage of substituents at the terminal-alkyne positions in alkynes.Contrastive experiments and DFT calculations show that the formation of a polycyclic system depends on the instantaneous coordination between the double ring[3.1.0]hexylplatinum carbine and the C=C isolated double bond.The innovation of this method mainly lies in the following aspects:1)in terms of the application of products:nitrogen heteropolyclic compounds with complex structure were synthesized by simple and easily available 1,6-enyne substrate in one step,which provided a new strategy for the synthesis of similar natural products and enriched enyne chemistry;2)In terms of product diversity,the strategy of adding substituents in different positions can lead to the synthesis of different products;3)In terms of mechanism,the reversible process of platinum carbine intermediates is used to capture intermediates and generate target products.Project 2:We found a method of synthesizing 1,6-alkynyl ketone with silver carbonate as catalyst.The main innovations of this research method are as follows:1)starting from the easily available 1,6-alkynyl ketone substrate,the nitrile was synthesized in one step;2)The mechanism is probably through the direct cleavage of the C-C triple bond;3)This study not only provides a new way for the application of alkynes in organic synthesis,but also provides a new insight for the study of the mechanism of nitriding reaction.