Development of a Redox-Active Ligand Framework: A Novel Approach towards Reactivity in C−H Functionalization Reactions Open Access

Putri, Marcella Abby (2016)

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The development of C−H functionalization chemistry has advanced significantly in recent years, allowing for more efficient methods for synthesizing complex molecules by forming C−C and C−N bonds from classically unreactive C−H bonds. Although second- and third-row Group IX transition metal catalysts dominate significant portions of the field for C−H functionalization chemistry, recent work by several groups have indicated new reactivity patterns using first-row transition metal catalysts with redox-active ligands. However, limitations to these catalysts include ease of use and inaccessibility. We hypothesize that the use of redox-active ligands with second- and third-row transition metals will allow us to access new reactivity that was previously only accessible by first-row transition metal catalysts. A method for synthesizing a new redox-active ligand scaffold has been developed in our lab. Plans to generate metal complex and assess its viability in C−H functionalization reactions are currently underway.

Table of Contents

Introduction. 1

I. Classic Methods to Form C−C and C−N Bonds. 1

II. Metallocarbenes. 2

III. Metallonitrenes. 7

IV. Emerging Methods in C−C and C−N Bond Formation. 10

Results and Discussion. 16

I. C−H Amination with Aryl Azides. 16

II. Development of a Redox-Active Ligand Framework. 20

III. Future Directions. 26

Experimental. 28

General Information. 28

I. Preparation of Azide 7. 29

II. Preparation of 5-tert-butyl Phebox Ligands. 31

III. Preparation of 4-tert-butyl Iridium(III) Phebox Complexes. 34

IV. Amination Reaction for Tetrahydroquinoline Formation. 36

V. Preparation of Ligand 23. 37

VI. HPLC Data. 45

References. 46

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