92623-83-1Relevant articles and documents
Lewis Base-Catalyzed Amino-Acylation of Arylallenes via C-N Bond Cleavage: Reaction Development and Mechanistic Studies
Xia, Ji-Bao,Yang, Yusheng,Yu, Zhi-Xiang,Zhang, Zheng-Bing
, p. 5419 - 5429 (2020/09/02)
Lewis base-catalyzed transformations of allenes have received much attention over the last decades. However, this type of reaction has so far been limited to activated allenes bearing an electron-withdrawing group. On the other hand, cleavage of an amide C-N bond to forge other chemical bonds has been widely reported but restricted to low atom economy due to the waste of the amine moiety of amides. We initiated a project of metal-catalyzed amino-acylation of allenes via cleavage of amide C-N bonds. Surprisingly, an amino-acylation of weakly activated aryl allenes was discovered via Lewis base catalysis, providing 2-methyl-3-aroylindole products, "privileged structures"in drug discovery. This is a unique example of Lewis base catalysis of weakly activated allenes, which was not reported yet. Extensive experimental and computational studies have been conducted to provide insight into the reaction mechanism. The nucleophilic addition of Lewis base catalyst to aryl allene is the rate-limiting step. A challenging [1,3]-proton transfer is realized by nitrogen anion intermediate assisted sequential [1,4]- and [1,6]-proton transfer in the reaction pathway.
Cyclooctatetraene: A Bioactive Cubane Paradigm Complement
Xing, Hui,Houston, Sevan D.,Chen, Xuejie,Ghassabian, Sussan,Fahrenhorst-Jones, Tyler,Kuo, Andy,Murray, Cody-Ellen P.,Conn, Kyna-Anne,Jaeschke, Kara N.,Jin, Da-Yun,Pasay, Cielo,Bernhardt, Paul V.,Burns, Jed M.,Tsanaktsidis, John,Savage, G. Paul,Boyle, Glen M.,De Voss, James J.,McCarthy, James,Walter, Gimme H.,Burne, Thomas H. J.,Smith, Maree T.,Tie, Jian-Ke,Williams, Craig M.
, p. 2729 - 2734 (2019/02/03)
Cubane was recently validated as a phenyl ring (bio)isostere, but highly strained caged carbocyclic systems lack π character, which is often critical for mediating key biological interactions. This electronic property restriction associated with cubane has been addressed herein with cyclooctatetraene (COT), using known pharmaceutical and agrochemical compounds as templates. COT either outperformed or matched cubane in multiple cases suggesting that versatile complementarity exists between the two systems for enhanced bioactive molecule discovery.
Application of hypervalent iodine reagent-mediated in preparation of indole derivatives
-
, (2018/11/22)
The invention relates to application of hypervalent iodine reagent-mediated in preparation of indole derivatives, in particular to the application of organic trivalent iodine reagent iodoyl benzene aminosulfonate in preparing N-protected 2-substituted indole compounds and indomethacin, zidometacin, pravadoline. The invention relates to the application of organic trivalent iodine reagent iodoyl benzene aminosulfonate in preparing N-protected 2-substituted indole compounds, and the reaction undergoes functional group exchange of a substrate. In addition, iodoyl benzene aminosulfonate plays two important roles in this application, as an oxidant and as Bronsted acid. The application has the advantages of good regioselectivity, wide substrate range, mild conditions, simple operation and amplification of experimental steps. The application of the organic trivalent iodine reagent iodoyl benzene aminosulfonate in the preparation of indomethacin, zidomeprin and pravadoline provided by the invention has the advantages of high synthesis efficiency, simple operation and the like.
