Synthesis and Evaluation of Novel Phenyl-Adamantane Dirhodium Catalyst for C-H Functionalization Restricted; Files Only

Abstract

Phthalimide-based dirhodium catalysts PTAD and TCPTAD are capable of catalyzing highly selective cyclopropanation and C-H functionalization reactions. However, their synthetic routes are difficult and risky to carry out. A novel phenyladamantyl (PHAD) dirhodium catalyst was developed that features a 3-step synthesis that is safer and more straightforward than the syntheses of phthalimide-based catalysts. A crucial step of the synthesis of PHAD is a tertiary C-H functionalization reaction of adamantane that has been optimized to 3^rd generation Davies Group methodologies. Dirhodium p-Br-PHAD was evaluated in a series of cyclopropanation and C-H functionalization reactions, exhibiting moderate levels of stereoselectivity and site selectivity. This work demonstrates that with further ligand optimization, dirhodium PHAD catalysts could offer a more accessible alternative to phthalimide-based dirhodium catalysts.

Table of Contents

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

1.1) Dirhodium-Catalyzed C-H Functionalization………………….…...……...……..………….1

1.2) Dirhodium PTAD and TCPTAD…………………………………………………......……....4

2.) Dirhodium PHAD Design and Synthesis………………………………………...……………6

2.1) Catalyst Design Philosophy.………………...…………………..…..………………………..6

2.2) Dirhodium PHAD Synthesis………………………………………………………………....8

2.2) Dirhodium PHAD Synthesis………………………………………………………………....8

2.2.1) Overview of Synthesis.………………...…………………..…..………………….………..8

2.2.2) Optimization of Adamantane C-H Functionalization…...…………..…………….………..8

2.2.3) Final Steps to Completed Catalyst…….…………………..…..………………….……….11

3.) Dirhodium PHAD Catalyst Evaluation………..……………………………………………..12

3.1) Optimization of Model Reaction……………………………………………………………12

3.2) Additional Test Reactions……..……………………………………………………………14

4.) Conclusions……………………..………………………………………………………...….15

5.) Experimental.……………....………...………………………………………………….…....18

5.1) General Considerations…………………………………….……………....………...……...18

5.2) Preparation of Diazo Compounds……………….……….……………………...…………..19

5.3) General Procedure for C-H Functionalization and Cyclopropanation Reactions…………...19

5.4) Site Selectivity Analysis ……………………………………………..……………………..27

5.5) HPLC Traces………………………..………………………….…...………………………29

5.5.1) Traces Corresponding to Table 1….…….…………………….…………………………..29

5.5.2) Traces Corresponding to Recrystallization and PHAD Ligand……………….…………..33

5.5.3) Traces Corresponding to Table 2….…….…………………….…………………………..37

5.5.4) Traces Corresponding to Table 3….…….…………………….…………………………..41

5.6) NMR Spectra……………………...….…….…………………….………………..………..43

6.) References……………………………………………..……………………………………..49

About this Honors Thesis

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School	Emory College
Department	Chemistry
Degree	B.S.
Submission	Honors Thesis
Language	English
Research Field	Chemistry, Organic
Keyword	C-H functionalization
Committee Chair / Thesis Advisor	Huw Davies, Emory University
Committee Members	Frank McDonald, Emory University Jose Soria, Emory University

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