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Asymmetric cyclization reactions through an enamine/acid cooperative approach. Synthesis of unsymmetrically functionalized benzoporphyrins

Deng, Yongming
http://rave.ohiolink.edu/etdc/view?acc_num=miami1406213121

Abstract Details

2014, Doctor of Philosophy, Miami University, Chemistry and Biochemistry.
The combination of enamine catalysis with metal catalysis, aiming to achieve organic transformations that cannot be accessed by enamine catalysis or metal catalysis independently, promises huge potential. The major obstacle in the development of enamine/metal Lewis acid combining catalysis is the incompatibility of the catalysts. The goal of this research is to solve this long lasting challenge and develop powerful asymmetric catalysts. Chapter one will provide a brief introduction to asymmetric catalysis and combing catalysis of enamine catalysis with transition metal catalysis. In Chapter two, the first application of arylamines in enamine catalysis is presented. The incompatibility of enamine catalysts and metal Lewis acid is solved by applying arylamines/acids cooperative catalysis. Through combination with either a metal Lewis acid or a chiral phosphoric acid, arylamines successfully catalyzed the asymmetric aldol reaction of cyclohexanone with both isatin and enones. Additionally, a highly chemo- and enantioselective three-component aza-Diels-Alder reaction was developed by combining arylamines with metal Lewis acids. In Chapter three, we devise a new type of chiral Lewis-acid-assisted Lewis acid catalyst formed from a metal Lewis acid and a chiral metal phosphate (MLA/M[P]3-LLA). A highly chemo- and enantioselective three-component aza-Diels-Alder reaction of cylic ketones (5, 6, and 7 membered) was successfully achieved by in situ prepared MLA/M[P]3-LLA. Preliminary structural studies have revealed that these LLA catalysts have a bimetallic center with bridging phosphate ligands. The Lewis acidity and stereoselectivity of the MLA/M[P]3-LLA catalysts can be easily tuned by changing either the Lewis acid co-catalyst or the chiral metal phosphate component, forming either homobimetallic or heterobimetallic catalysts. In Chapter four, a trio catalysis system involving arylamines, BINOL-phosphoric acids, and metal Lewis acids is first disclosed. By using this trio catalyst, a series of optically active functionalized dihydropyridines was successfully synthesized through a highly chemo- and enantioselective three-component aza-Diels-Alder reaction of substituted cinnamaldehyde, cyclic ketone, and arylamine. In Chapter five, a series of unsymmetrically functionalized benzoporphyrins was successfully synthesized.
Hong Wang, Ph.D (Advisor)
Michael Novak , Ph.D (Committee Chair)
Scott Hartley, Ph.D (Committee Member)
Shouzhong Zou, Ph.D (Committee Member)
Annette Bollmann, Ph.D (Committee Member)
163 p.
Chemistry
cooperative catalysis; enamines; Lewis acids; multicomponent reactions; aza-Diels-Alder reactions

Recommended Citations

Citations

  • Deng, Y. (2014). Asymmetric cyclization reactions through an enamine/acid cooperative approach. Synthesis of unsymmetrically functionalized benzoporphyrins [Doctoral dissertation, Miami University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=miami1406213121

    APA Style (7th edition)

  • Deng, Yongming. Asymmetric cyclization reactions through an enamine/acid cooperative approach. Synthesis of unsymmetrically functionalized benzoporphyrins. 2014. Miami University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=miami1406213121.

    MLA Style (8th edition)

  • Deng, Yongming. "Asymmetric cyclization reactions through an enamine/acid cooperative approach. Synthesis of unsymmetrically functionalized benzoporphyrins." Doctoral dissertation, Miami University, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=miami1406213121

    Chicago Manual of Style (17th edition)

miami1406213121
514
© 2014, all rights reserved.
This open access ETD is published by Miami University and OhioLINK.