@article{Formanilide-Directed:7523,
      recid = {7523},
      author = {Durfee, Nathaniel D},
      title = {Asymmetric Total Syntheses of the Fontonamides Via  Formanilide-Directed Palladium-Catalyzed C-H  Functionalization and Synthetic Studies Towards  (+)-Welwitindolinone A},
      publisher = {University of Chicago},
      school = {Ph.D.},
      address = {2023-08},
      pages = {436},
      abstract = {Using a novel route that takes advantage of the directing  ability of the natural formanilide directing group, the  first total synthesis of two members of the hapalonamide  family,  (-)-fontonamide and (-)-dechlorofontonamide, are  reported herein. The syntheses are highly convergent,  coupling the A ring formanilide fragment and the D ring  highly-decorated-cyclohexanone fragment through a  Friedel-Crafts reaction and a ortho-directed C-H  functionalization. Both syntheses have been rendered  asymmetric. A third member of the hapalonamide family.  13-hydroxy dechlorofontonamide, was also synthesized,  however it was determined upon its synthesis that the  original isolation paper had misassigned the isolated  compound, which was in actuality fontonamide. This thesis  also describes the synthetic effort undertaken towards  welwitindolinone A, with the goal of using a novel  intramolecular palladium-mediated alkenylation to create  the core cyclobutene ring of the compound. This reaction  was successful in model studies, but ultimately failed on  the fully-decorated molecule. Finally, this thesis  describes the successful development of a novel  1,1-disubstituted diene for use in the Diels-Alder  reaction. The novel diene allows access to 6-substituted  and 6,6-disubstituted cyclohexenones and 6-substituted  5,6-dihydropyran-2-ones. The synthesis of the diene is  highly scalable and operationally facile, and kinetics  experiments show the reactivity of the diene is high  compared to other highly active dienes.  },
      url = {http://knowledge.uchicago.edu/record/7523},
      doi = {https://doi.org/10.6082/uchicago.7523},
}