| This paper is divided into two parts.First part,a new method of synthesizing thiazolylidene derivatives was described.Thiazolylidene derivatives are widely applied to biological and medical fields,and thiazolylidene derivatives could combine with many bio-enzymes or receptors with a variety of biological activities.Therefore,thiazolylidene compounds are widely used in medicine,pesticides and other fields,so it’s worth researching.Second part of this paper,a new method of synthesis 3-ylideneoxindoles was mentioned,as a class of important organic synthetic intermediate,3-ylideneoxindoles have important applications in the field of asymmetric catalytic synthesis,especially to synthesis spiro compounds.Nowadays,3-ylideneoxindoles are still attracting a large number of chemical workers continue to research.In first part,the applications of β-ketothioamides(KTAs)in the organic synthesis reactions reported in the literature were reviewed.The catalytic oxidation system of tetrabutylammonium iodide(TBAI)/t-butylhydroperoxide(TBHP)was described.At last,various synthetic routes and applications to thiazolylidene derivatives and thiazole derivatives in the literature were reviewed.A novel method based on reaction of β-ketothioamides with malononitrile to construct thiazolylidenes has been developed under room temperature.The TBAI and TBHP were applied in this method.Reaction conditions: KTAs : malononitril = 1 : 1.5,TBAI as catalyst(0.1 equiv),TBHP as oxidant(2 equiv),Et3 N as base(1 equiv)in EtOH at room temperature.This approach presents broad substrate scope and excellent functionality tolerance.To explore the reaction mechanism for this transformation,some control experiments were conducted.All the newly synthesized compound structures have been characterized by 1H NMR,13 C NMR and HRMS,and the single crystal of the product 3b has been cultured to determine the precise structure of the target compound.The method has the advantages of mild condition,simple operation,fast and efficient,good selectivity and simple post-processing.In second part,an effective method based on reaction of isatin with ethyl isocyanoacetate to construct 3-ylideneoxindoles has been developed by catalyst CuI.The nitrogen atom of the isatin was protected by methyl group.To showcase the practicality of our method,the reaction of 5-chloro-1-methly isatin was scaled up to 10 mmol and the desired product was obtained without a significant loss in yield. |
