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Peptide-Mediated Asymmetric Cross-Coupling and Related Studies
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| 자료유형 | 학위논문 |
|---|---|
| 서명/저자사항 | Peptide-Mediated Asymmetric Cross-Coupling and Related Studies. |
| 개인저자 | Chinn, Alex James. |
| 단체저자명 | Yale University. Chemistry. |
| 발행사항 | [S.l.]: Yale University., 2019. |
| 발행사항 | Ann Arbor: ProQuest Dissertations & Theses, 2019. |
| 형태사항 | 474 p. |
| 기본자료 저록 | Dissertations Abstracts International 81-04B. Dissertation Abstract International |
| ISBN | 9781088382561 |
| 학위논문주기 | Thesis (Ph.D.)--Yale University, 2019. |
| 일반주기 |
Source: Dissertations Abstracts International, Volume: 81-04, Section: B.
Advisor: Miller, Scott J. |
| 이용제한사항 | This item must not be sold to any third party vendors. |
| 요약 | Herein we report the development of multifunctional guanidinylated peptide ligands and their application in asymmetric copper catalyzed cross-coupling. Initial studies described in Chapter 2 focus on the desymmetrization of a symmetric diarylmethine scaffold which contains enantiotopic aryl bromides that are three bonds removed from the prochiral center. High levels of enantioinduction and good yields were achieved using several malonate nucleophiles (up to 93:7 er and 76% yield). Mechanistic studies suggest the peptide acts as a bifunctional ligand, wherein the C-terminal carboxylate interacts with the substrate through a bridged Cs ion. Chapter 3 expands upon these studies and describes the first asymmetric intermolecular metal catalyzed C-O cross-coupling reaction. Among these phenols, a range of both electronic and steric perturbations were tolerated and provided the desired diaryl ether in good yield (up to 68% yield and 99:1 er). In addition, reasonable chemoselectivity was demonstrated for phenols with multiple nucleophilic functional groups.Chapter 4 discusses efforts towards achieving the site-selective arylation of tyrosine containing peptides by using aspartic acid as a directing group. As a proxy for peptides containing four tyrosine residues, optimization efforts were conducted as a series of competition studies performed using four tetrapeptides, which compete for a limited amount of aryl halide. These results were then successfully applied in peptides containing multiple tyrosine residues. |
| 일반주제명 | Chemistry. |
| 언어 | 영어 |
| 바로가기 | 
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