Synthetic approaches to a hypervalent trigonal bipyramidal carbon species and a versatile reagent for the oxidation of primary and secondary alcohols to aldehydes and ketones
Henderson, Craig Conger
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https://hdl.handle.net/2142/20222
Description
Title
Synthetic approaches to a hypervalent trigonal bipyramidal carbon species and a versatile reagent for the oxidation of primary and secondary alcohols to aldehydes and ketones
Author(s)
Henderson, Craig Conger
Issue Date
1991
Doctoral Committee Chair(s)
Deuman, Scott E.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Language
eng
Abstract
The synthesis of a novel ortho-bridged triarylmethanol, 6-(1,1-dimethylethyl)-12c-hydroxy-4,8-dioxa-4H,8H-dibenzo- (cd,mn) pyren-12(12cH)-one, is described in Part I. The key step involves an intramolecular Friedel-Crafts reaction of a triarylmethyl cation. Some reactions of this methanol derivative are presented as part of an attempted synthesis of a hypervalent (10-C-5) trigonal bipyramidal carbon species.
Other approaches to a hypervalent trigonal bipyramidal carbon species from spiro (anthracene-9,1$\sp\prime$-phthalan) derivatives are presented in Part II. The electronic and geometric factors of the ligands in the target hypervalent carbon species are discussed in terms of known ligand-induced stabilization of hypervalent species of higher row main group elements. Stabilization of the hypervalent bond by delocalization of the excess electron density in the three-center, four-electron (3c-4e) bond onto a bidentate $\pi$-acceptor ligand in the equatorial plane of the trigonal bipyramidal 10-C-5 species is emphasized. The synthesis and reactions of the spiro (anthracene-9,1$\sp\prime$-phthalan) precursors is given along with a summary of the attempts to convert these precursors to hypervalent 10-C-5 species. The synthetic value of a mercuration/halogenation reaction for the regiospecific addition of an iodine to an arene is illustrated in the synthesis of one of the precursors, a novel ortho-bridged triarylmethyl trifluoromethylsulfonate.
Another example of the mercuration/halogenation reaction of an arene is given in Part III which describes the large scale synthesis of 4-(1,1-dimethylethyl)-2-iodobenzoic acid, the precursor to 1,1,1-tris(acetoxy)-6-(1,1-dimethylethyl)-1,1-dihydro-1,$ 2$-benziodoxol-3(1H)-one. The use of this 12-I-5 triacetoxyperiodinane, which is a derivative of the so-called Dess-Martin Periodinane, as a reagent for the oxidation of primary and secondary alcohols to aldehydes and ketones is also described. The advantages of the tert-butylated triacetoxyperiodinane compared to the unsubstituted Dess-Martin triacetoxyperiodinane are discussed in terms of ease of preparation, increased solubility, and decreased rate of decomposition of the 10-I-4 iodinane oxide precursor at its melting point. Several examples of oxidations of alcohols with 12-I-5 triacetoxyperiodinanes and 10-I-4 iodinane oxides are given, and a possible mechanism for these reactions is discussed.
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