Synthetic Applications of Dirhodium(II) Catalysis Restricted; Files Only

Hicks, Elliot (Spring 2020)

Permanent URL: https://etd.library.emory.edu/concern/etds/8336h297q?locale=en
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Abstract

Dirhodium(II) catalyzed reactions have proven to be synthetically useful tools for transforming bonds that are traditionally difficult to functionalize. These atypical transformations allow for the rapid construction of molecules which would otherwise take many steps to build. This study showcases two applications of dirhodium(II) catalysis. The first application focuses on the functionalization of organosilicon compounds as a way to rapidly and selectively incorporate silicon, which has potential applications in the pharmaceutical industry. The second application focuses on performing one step in a sequence in an enantioselective fashion. The resulting enantiomerically enriched compounds could be carried forward to make enantiomerically enriched endoperoxides, which have applications in antimalarial drug discovery. 

Table of Contents

1.) Introduction......................................................................................................................1

1.1) The Importance of Stereochemistry and Stereoselective Synthesis................................1

1.2) Rhodium Catalyzed Decomposition of Diazonium Compounds......................................2

1.3) Synthetic Utility of Carbenes/Carbenoids & Davies Group Catalyst Development.........5

2.) First Application: C-H Functionalization of Cyclic Organoslianes....................................7

3.) Second Application: Kinetic Resolution via Cyclopropanation of 2-phenyl-2,3-

dihydrofuran.........................................................................................................................16

4.) Conclusions.....................................................................................................................24

5.) Experimental...................................................................................................................25

5.1) General Procedure 1 for C–H Functionalization Reactions...........................................25

5.1.1) X-Ray Crystal Structure of Compound 6....................................................................45

5.2) Catalyst Screen for Diastereoselective Reactions.........................................................46

5.3) General Procedure 2 for Cyclopropanation Reactions..................................................47

5.3.1) Representative 1H NMR Spectra................................................................................49

5.4) Dihydrofuran HPLC Traces...........................................................................................50

5.4.1) Traces Corresponding to Figure 3.2...........................................................................51

5.4.2) Traces Corresponding to Figure 3.3...........................................................................53

5.4.3) HPLC Trace for Figure 3.5..........................................................................................56

6.) References......................................................................................................................56 

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