A new synthetic route to clavilactone B, a naturally occurring inhibitor of epidermal growth factor receptor (EGFR) tyrosine kinase, is disclosed. The route features a sequential samarium-mediated radical cyclization-fragmentation of an indanone derivative, which provides rapid access to a 10-membered carbocyclic motif fused to an aromatic ring.
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http://dx.doi.org/10.1021/ol503356m | DOI Listing |
J Org Chem
November 2021
Department of Chemistry, Fu Jen Catholic University, 510 Zhongzheng Road, Xinzhuang District, New Taipei City, 24205 Taiwan.
Various -(2-bromo-allyl) benzamides were used as the starting materials to study vinyl radical cyclization reactions. The vinyl radicals underwent ipso-cyclization, fragmentation, and cyclization reactions to produce β-aryl-γ-lactams with the carbonyl group remaining intact. To further study this cascade radical reaction, vinyl radicals were generated by the addition of a tributyltin radical to alkyne moieties, followed by radical ipso-cyclization, fragmentation, cyclization, and β-scission reactions with the production of a series of α,β-unsaturated-β-aryl-γ-lactam derivatives.
View Article and Find Full Text PDFOrg Lett
July 2021
Department of Chemistry, University of Cape Town, Rondebosch, Cape Town, 7700, South Africa.
The synthesis of symmetrical 3,3'-bisoxindoles from simple acyclic β-oxoanilides is reported. The described method forges three new C-C bonds in a single step via a sequential Mn(OAc)2HO mediated oxidative radical cyclization-fragmentation-dimerization process. The scope of this reaction is demonstrated in the preparation of a variety of 3,3'-bisoxindoles, as well as its application toward the formal synthesis of the Calycanthaceae alkaloid, (±)-folicanthine.
View Article and Find Full Text PDFOrg Biomol Chem
February 2019
Key Laboratory of Bioorganic Chemistry and Molecular Engineering, Ministry of Education, Beijing National Laboratory for Molecular Science, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
The [6,5,5] tricyclic fungal metabolite galiellalactone is a Michael acceptor that has been demonstrated to be a covalent inhibitor for Signal Transducer and Activator of Transcription 3 (STAT3). Recognizing the ring strain associated with the skeleton of this natural product, we utilized 1R-5S-bicyclo[3.1.
View Article and Find Full Text PDFJ Am Chem Soc
February 2018
Department of Chemistry, University of California, Irvine, California 92697-2025, United States.
The first total synthesis of a chromodorolide marine diterpenoid is described. The core of the diterpenoid is constructed by a bimolecular radical addition/cyclization/fragmentation cascade that unites two complex fragments and forms two C-C bonds and four contiguous stereogenic centers of (-)-chromodorolide B in a single step. This coupling step is initiated by visible-light photocatalytic fragmentation of a redox-active ester, which can be accomplished in the presence of an iridium or a less-precious electron-rich dicyanobenzene photocatalyst, and employs equimolar amounts of the two addends.
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