Allylic C-H Functionalization Studies on Allylbenzene Derivatives Open Access

Abstract

Selective C-H functionalization has been an emerging field within organic chemistry in the past few decades due to its potential for more efficient syntheses of essential compounds relevant to the fields of medicine and pharmaceuticals. Allylic C-H functionalization has become an increasingly important area of chemistry research as it presents novel possibilities for efficient and bio sustainable reactions in the laboratory. This study investigates the utilization of Iridium(III)-catalyzed C-H sulfonamidation on allylbenzene derivatives using tosyl azide as the nitrogen source. Subsequently, the study investigates and discusses preliminary results from Iridium(III)-catalyzed C-H amination with a benzyl carbamate as the nitrogen source. The impact of the results is the development of a more efficient and bio sustainable pathway for sulfonamidation, a process which can be applied for more efficient drug synthesis and mechanistic design in the future. 

Table of Contents

Contents:

Introduction 1 

Results 6 

Further Studies 12 

Conclusion 17 

Supplemental Information 17 

References 35 

Figures:

Figure 1 White et. al. - Oxidative C-H functionalization 1 

Figure 2 Cossy et. al. – Cyclic amine synthesis using RhCp* 2 

Figure 3 Tanaka et. al. – Selective coordination of the π -allyl intermediate onto internal olefins 3 

Figure 4 Blakey et. al., Glorius et. al. - Allylic C-H functionalization studies 3 

Figure 5 Reaction pathway for allylic C-H functionalization using an external oxidant – AgOAc 4 

Figure 6 Blakey et. al., Rovis et. al. - Allylic C-H amidation using dioxazolones 5 

Figure 7 Substrate Scope - Steven Chen 8 

Figure 8 Substrate Scope - Amaan Kazerouni, Taylor Nelson, Kim Sharp 9 

Figure 9 Intended product of benzyl carbamate insertion on allylbenzene 12 

Figure 10 Synthesis of a bis-trifluoromethyl-substituted compound 13 

Figure 11 Synthesis of OPiv-NH-Cbz 15 

Figure 12 Synthesis of Ts- NH-OPiv 16 

Tables: 

Table 1 Sulfonamidation reaction on allylbenzene – optimization trials 7 

Table 2 Benzyl carbamate insertion initial trials 14 

Table 3 Benzyl carbamate insertion with OPiv-NH-Cbz 15 

Schematics: 

Schematic 1 Sulfonamidation reaction pathway 11 

About this Honors Thesis

Rights statement

• Permission granted by the author to include this thesis or dissertation in this repository. All rights reserved by the author. Please contact the author for information regarding the reproduction and use of this thesis or dissertation.

School	Emory College
Department	Chemistry
Degree	B.A.
Submission	Honors Thesis
Language	English
Research Field	Chemistry, Biochemistry Chemistry, Organic Chemistry, Inorganic
Keyword	Chemistry Functionalization
Committee Chair / Thesis Advisor	Simon Blakey, PhD, Emory University
Committee Members	Douglas Mulford, PhD, Emory University Benjamin Reiss, PhD, Emory University

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