Site-Selective and Enantioselective C-H Functionalization of Unactivated C–H Bonds in the Presence of Nitrogen Functionality Público

Abstract

The rhodium-catalyzed C-H functionalization of unactivated C-H bonds by means of donor/acceptor carbene-induced C-H functionalization was extended to substrates containing nitrogen functionality. The optimum nitrogen protecting group was the phthalimido group and aryldiazoacetates were used as the precursors to the donor/acceptor carbenes. By using Rh2(S-2-Cl-5-BrTPCP)4 as catalyst, selective C-H functionalization occurred at the most sterically accessible methylene site, whereas the desymmetrization of cyclopentylamine and cyclohexylamine derivatives was possible when Rh2(S-TPPTTL)4 was used as a catalyst.

Table of Contents

Table of Contents

Site-selective and Enantioselective C-H Functionalization of Unactivated C-H Bonds in the Presence of Amine Functionalities………………………………………………………….…...1

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

2 Results and Discussion…………………………......………………………………….……….4

2.1 The Discovery of Protecting Groups………………..……………………………….4

2.2 The Study about the Distance from the Primary Amines……………..………..…13

2.3 Expansion of the Scope to Tertiary Sites……………………………………..….…17

2.4 Further Support of Asymmetric Induction………………………..………………22

2.5 Desymmetrization of Cyclic Systems……………………………………………....27

2.6 Reaction Scope with Aryldiazoacetates………………………………..…..………31

3 Conclusions and Future Directions……………......………………………………….…..….32

4 Experimental Part…………………….………………………………………………………33

4.1 General Procedures for Substrates and C-H Insertion Products……...…..……...33

4.2 Experimental Part for Substrates….………...………...…………………………...36

4.4 Experimental Part for Aryldiazoacetate……............……………………………...42

4.5 Experimental Part for C-H Insertion Products.........……………………………...43

Reference………………………………………………………………………………………..54

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School	Emory College
Department	Chemistry
Degree	B.S.
Submission	Honors Thesis
Language	English
Research Field	Chemistry, Organic
Palavra-chave	C-H Functionalization Organometallics
Committee Chair / Thesis Advisor	Huw Davies, Emory University
Committee Members	Effrosyni Seitaridou, Emory University Matthew Weinschenk, Emory University Brenda Harmon, Emory University Frank McDonald, Emory University

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