Azaspirocyclic compounds have gained attention in chemistry and drug discovery fields. In this manuscript, the development of a Pd-catalyzed dearomative azaspirocyclization of bromoarenes bearing an aminoalkyl group with N-tosylhydrazones is described. The present method enables azaspirocyclization with the introduction of carbon substituents, achieving the convergent synthesis of 1-azaspirocycles. This method allowed furan, thiophene, and naphthalene cores to generate the corresponding 1-azaspirocycles. The obtained azaspirocycles from furans were further elaborated via an acid-catalyzed rearrangement to afford 1-azaspirocyclopentenones. File list (2)download file view on ChemRxiv 2021YanagimotoUwabe.pdf (1.33 MiB) download file view on ChemRxiv 2021YanagimotoUwabe_SI.pdf (50.13 MiB)

A palladium-catalyzed 1,4-carboamination of bromoarenes with diazo compounds and amines was developed. This reaction proceeds through a palladium-carbene that then generates a π-benzylpalladium intermediate, forming ipso C–C and para C–N bonds on bromoarenes in a regioselective manner. The successful application of this transformation to the rapid synthesis of an antitumor agent demonstrates its synthetic utility.

1-Azaspirocyclic compounds have gained attention in chemistry and drug discovery fields. In this manuscript, the development of a Pd-catalyzed dearomative azaspirocyclization of bromoarenes bearing an aminoalkyl group with <i>N</i>-tosylhydrazones is described. The present method enables azaspirocyclization with the introduction of carbon substituents, achieving the convergent synthesis of 1-azaspirocycles. This method allowed furan, thiophene, and naphthalene cores to generate the corresponding 1-azaspirocycles. The obtained azaspirocycles from furans were further elaborated <i>via</i> an acid-catalyzed rearrangement to afford 1-azaspirocyclopentenones.

With increasing risks faced by financial firms and markets, text mining is playing more and more important role. However, because of the complexity between a text and the consequences caused by the text, it is hard for traditional text mining techniques to meet the needs. In order to solve this problem, we focus on the employment of intelligent agents to enhance the capability of text analysis. In our system, various classes of intelligent agents are proposed for financial risk early warning. The text mining agent gives influence measurement, the relationship agent generates relationship measurement between the text and the target, and the reliability agent measures whether the text is trustable or not. Collaboration within such agents is able to produce more effective and accurate early warning messages.

A palladium-catalyzed 1,4-carboamination of bromoarenes with diazo compounds and amines was developed. This reaction proceeds through a palladium-carbene that then generates a π-benzylpalladium intermediate, forming ipso C–C and para C–N bonds on haloarenes in a regioselective manner. The nature of this reaction as a multi-component reaction and its high regioselectivity can lead to a rapid construction of a range of para-substituted anilines. The successful application of this transformation to the rapid synthesis of an anti-tumor agent demonstrates its synthetic utility.