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THE DEVELOPMENT OF NOVEL AND CONVENIENT TRANSFORMATIONS OF AZIRIDINES

HANCOCK, MATTHEW THOMAS
http://rave.ohiolink.edu/etdc/view?acc_num=ucin1054137190

Abstract Details

2003, PhD, University of Cincinnati, Arts and Sciences : Chemistry.
Several novel transformations of aziridines to 1,2-diamines, 2-oxazolidinones, and benzodiazepines have been developed. Previous work in the Pinhas group showed that an aziridine could be reacted with lithium iodide, iron carbonyl, and trimethylamine oxide to yield a 1,2-diamine. This reaction has been extended to include various amine oxides, several different aziridines, and a variety of metal carbonyls. A novel synthesis of 1,2-diamines has been developed, in which, an aziridine is treated with an iminium salt in the presence or absence of lithium iodide. This reaction has also been extended to include various iminium salts and several different aziridines. The stereochemistry and mechanism of both of these reactions have also been investigated. It has also been discovered that when an aziridine is treated with lithium iodide and then quenched with carbon dioxide, the product is an oxazolidinone. This reaction has been examined using several different aziridines. The reaction is catalytic in lithium iodide. In fact, a catalytic amount of lithium iodide improves the stereoselectivity of the reaction. It has been determined that hexamtheylphosphoramide can be added to the reaction mixture to improve the regiochemistry of the product oxazolidinone. When an aziridine is treated with a phenyl-substituted iminium salt, the expected 1,2-diamine is generated. However, when an aziridine is treated with a phenyl-substituted amine oxide or gem-aminoether, a benzodiazepine is produced. A mechanism is proposed based on the preliminary results.
Dr. Allan Pinhas (Advisor)
157 p.
Chemistry, Organic
aziridines; diamines; oxazolidinones; benzodiazepines; carbon dioxide insertion

Recommended Citations

Citations

  • HANCOCK, M. T. (2003). THE DEVELOPMENT OF NOVEL AND CONVENIENT TRANSFORMATIONS OF AZIRIDINES [Doctoral dissertation, University of Cincinnati]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1054137190

    APA Style (7th edition)

  • HANCOCK, MATTHEW. THE DEVELOPMENT OF NOVEL AND CONVENIENT TRANSFORMATIONS OF AZIRIDINES. 2003. University of Cincinnati, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=ucin1054137190.

    MLA Style (8th edition)

  • HANCOCK, MATTHEW. "THE DEVELOPMENT OF NOVEL AND CONVENIENT TRANSFORMATIONS OF AZIRIDINES." Doctoral dissertation, University of Cincinnati, 2003. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1054137190

    Chicago Manual of Style (17th edition)

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© 2003, all rights reserved.
This open access ETD is published by University of Cincinnati and OhioLINK.