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Model studies for the total synthesis of vancomycin and related compounds using organoiron and organoruthenium complexes

Park, Jewn-Giew
http://rave.ohiolink.edu/etdc/view?acc_num=case1059674409

Abstract Details

1992, Doctor of Philosophy, Case Western Reserve University, Chemistry.
In an effort to gain access to the "upper half" of molecules belonging to the vancomycin class, various Fe+Cp complexes of diaryl ethers and triaryl diethers were synthesized in high yield under mild conditions via nucleophilic substitution reactions between (1,3-dichlorobenzene)Fe+Cp PF6- and various aryl oxides, which include aryl amino acids. The reactions between triaryl diether-Fe+Cp complexes and glycine enolate equivalents and subsequent rearomatization were attempted without success. Photolysis of the Fe+Cp complexes of diaryl ethers and triaryl diethers gave demetallated products with no detectable racemization in the amino acid side chains, providing a useful method for the construction of aryl ethers. Several (polychlorobenzene)Ru+Cp complexes were synthesized by treatment of polychloroarenes with (CH3CN)3Ru+Cp PF6-. In a number of cases the analogous iron complexes can not be prepared. Similar reactivity has been found for Fe+Cp and Ru+Cp toward aryloxides, but the chloride attached to the benzene ring in (chloroarene)CpFe+ complexes could be displaced by carbanions, whereas (chloroarene)Ru+Cp did not undergo nucleophilic substitution reactions with the same carbanions. In an effort to prepare the "upper right" moiety of a model for ristocetin A, optically active 4-chlorophenylalanine derivatives and 3-hydroxyphenylglycine derivatives were synthesized by the Evans method. Treatment of 4-chlorophenyl-alanine derivatives with (CH3CN)3RuCpPF6 gave (chloroarylamino acid)Ru+Cp in high yield under mild conditions. Ru+Cp complexes of 4-chlorophenylalanine derivatives underwent nucleophilic substitution reactions with 3-hydroxyphenylglycine derivatives to give the precursors of the "upper right" section of ristocetin A. Photolytic demetallation in acetonitrile afforded both demetallated diaryl ethers and (CH3CN)3Ru+Cp in high yield without racemization in the amino acid side chains. The use of a 2-bromoethyl ester as a protecting group for the amino acid proved to be problematic due to the unexpected formation of 2-hydroxyethyl ester during attempted deprotection. Thus, a more reliable protecting group is desired. Attempted peptide cyclizations using the standard Curtius method, the active ester method, the DPPA method, and various other coupling methods were unsuccessful
Anthony Pearson (Advisor)
177 p.
Chemistry, Organic
Vancomycin; Organoiron and organoruthenium complexes

Recommended Citations

Citations

  • Park, J.-G. (1992). Model studies for the total synthesis of vancomycin and related compounds using organoiron and organoruthenium complexes [Doctoral dissertation, Case Western Reserve University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=case1059674409

    APA Style (7th edition)

  • Park, Jewn-Giew. Model studies for the total synthesis of vancomycin and related compounds using organoiron and organoruthenium complexes. 1992. Case Western Reserve University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=case1059674409.

    MLA Style (8th edition)

  • Park, Jewn-Giew. "Model studies for the total synthesis of vancomycin and related compounds using organoiron and organoruthenium complexes." Doctoral dissertation, Case Western Reserve University, 1992. http://rave.ohiolink.edu/etdc/view?acc_num=case1059674409

    Chicago Manual of Style (17th edition)

case1059674409
617
© 1992, all rights reserved.
This open access ETD is published by Case Western Reserve University School of Graduate Studies and OhioLINK.