Optimization of Rh2(S-TPPTTL)4 Through Ligand Diversification Öffentlichkeit
Kirby, Randall (Spring 2021)
Published
Abstract
Discovering new ways to alter the classically inert C-H bond at different positions in a molecule has proven to be a valuable method to synthesize several complex structures. Dirhodium catalysts have been shown to perform these alterations with high yield and stereoselectivity. One of the most notable catalysts with promising reactions is the Rh2(tetra-phenyl-phthalimido-tertbutyl-leucino)4 catalyst (Rh2(TPPTTL)4). This catalyst has been shown to catalyze cyclopropanations and highly stereo-specific C-H functionalizations. A key factor in dictating this catalyst’s specificity is its C4 symmetry and large steric bulk, which was chosen as a promising area for optimization. Further optimization studies of this catalyst were conducted to broaden its scope of reactions and study the structure of the catalyst’s active site. This was achieved by increasing the overall bulk of the catalyst and the steric demand close to the catalyst’s active site.
Table of Contents
1. INTRODUCTION
1.1) The Biological Relevance of Stereoselective Synthesis
Figure 1.1.1
Figure 1.1.2
1.2) Dirhodium catalysts
Figure 1.2.1
Figure 1.2.2
1.3) C-H Functionalization
Figure 1.3.1
Figure 1.3.2
1.4) The Rh2(TPPTTL)4 Catalyst
Figure 1.4.1
2) MANIPULATING THE TPPTTL LIGAND
2.1) Synthetic Scheme
Figure 2.1.1
Figure 2.1.2
Figure 2.1.3
2.2) Synthetic Steps
Figure 2.2.1
Figure 2.2.2
Figure 2.2.3
Figure 2.2.4
Figure 2.2.5
Figure 2.2.6
2.3) Preparation for Manipulation via Suzuki Coupling
Figure 2.3.1
Figure 2.3.2
2.4) Suzuki Coupling Methodology
Figure 2.4.1
Figure 2.4.2
Figure 2.4.3
Figure 2.4.4
3) CATALYST CHARACTERIZATION
3.1) NMR
Figure 3.1.1
3.2) X-ray Crystallography
Figure 3.2.1
3.3) Mass Spectrometry
Figure 3.3.1
4) ASSESSING THE SELECTIVITY OF THE TPPTTL VARIANTS
Figure 4.1.1
Figure 4.1.2
Figure 4.1.3
Figure 4.1.4
Figure 4.1.5
Figure 4.1.6
4.2) Rh2(S-p-Br-TPPTTL)4
Figure 4.2.1
Figure 4.2.2
4.3) Rh2(S-3,5-m-Br-TPPTTL)4
Figure 4.3.1
Figure 4.3.2
4.4) Rh2(S-p-tbutyl-TPPTTL)4
Figure 4.4.1
Figure 4.4.2
4.5) Rh2(S-p-bisCF3-TPPTTL)4
Figure 4.5.1
Figure 4.5.2
4.6) Rh2(S-p-mesityl-TPPTTL)4 Catalyst
Figure 4.6.1
Figure 4.6.2
4.7) Rh2(S-3,5-m-ph-TPPTTL)4
Figure 4.7.1
Figure 4.7.2
4.8) Rh2(S-3,5-m-bisCF3-TPPTTL)4
Figure 4.8.1
Figure 4.8.2
5) CONCLUSION
6) EXPERIMENTAL
7) HPLC AND NMR DATA
8) REFERENCES
About this Honors Thesis
School | |
---|---|
Department | |
Degree | |
Submission | |
Language |
|
Research Field | |
Stichwort | |
Committee Chair / Thesis Advisor | |
Committee Members |
Primary PDF
Thumbnail | Title | Date Uploaded | Actions |
---|---|---|---|
|
Optimization of Rh2(S-TPPTTL)4 Through Ligand Diversification () | 2021-05-05 09:41:32 -0400 |
|
Supplemental Files
Thumbnail | Title | Date Uploaded | Actions |
---|