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The Dendritic Effect on Enantioselectivity of Organocatalytic Reactions and the Effect of Local Compaction on a Titanium Mediated Allylation of Aldehydes

McDaniel, Christopher George
http://rave.ohiolink.edu/etdc/view?acc_num=osu1281293828

Abstract Details

2010, Doctor of Philosophy, Ohio State University, Chemistry.
The synthesis, study and catalytic properties of chiral terminated dendrons based on an intramolecularly folded pyridine-2,6-dicarboxamide branch unit is reported. Two differently terminated chiral dendrons were prepared and studied for their chiroptical properties: 1.) N(π)-methyl histidine dendrons were prepared and tested as organocata-lysts in the kinetic resolution of secondary alcohols and an intramolecular acyl rear-rangement of oxindoles to generate all carbon, quaternary stereocenters, and 2.) bi-phenyl and tetra-phenyl-core-based, chiral terminated dendrons were synthesized and tested for their catalytic properties in the titanium mediated, asymmetric addition of allyl-tributyltin to aldehydes. In the former project (organocatalysis), the dendrons were, after much synthetic difficulty, synthesized up to their second generation and exhibited a slightly positive dendrimer effect from G0 to their second generation hierarchy. Using circular dichroism (CD) spectroscopy, the dendrons exhibited a positive Cotton-effect (CE) (P-helical bias) that was enhanced not only from the first to second generation, but also from organic to aqueous solvents. In the latter project (asymmetric allylation of al¬dehydes), various amide termini bi/tetra-phenyl core-based dendrons were prepared and showed a cooperative effect (in terms of enantioselectivity) when the tetraphenyl core was used. CD studies showed that the dendrons, when attached to the aforementioned cores, developed a bias toward an M-helical sense, which was much more pronounced in the tetraphenyl dendron.
Jonathon R Parquette (Advisor)
Christopher Hadad (Committee Member)
Jovica Badjic (Committee Member)
William Ray (Committee Member)
332 p.
Chemistry; Organic Chemistry
Dendrimers; dendrons; organocatalysis; kinetic resolution; allylation

Recommended Citations

Citations

  • McDaniel, C. G. (2010). The Dendritic Effect on Enantioselectivity of Organocatalytic Reactions and the Effect of Local Compaction on a Titanium Mediated Allylation of Aldehydes [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1281293828

    APA Style (7th edition)

  • McDaniel, Christopher. The Dendritic Effect on Enantioselectivity of Organocatalytic Reactions and the Effect of Local Compaction on a Titanium Mediated Allylation of Aldehydes. 2010. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1281293828.

    MLA Style (8th edition)

  • McDaniel, Christopher. "The Dendritic Effect on Enantioselectivity of Organocatalytic Reactions and the Effect of Local Compaction on a Titanium Mediated Allylation of Aldehydes." Doctoral dissertation, Ohio State University, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=osu1281293828

    Chicago Manual of Style (17th edition)

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This open access ETD is published by The Ohio State University and OhioLINK.