Expanding The Scope of Reactions and Applications for Dirhodium(II) Tetracarboxylate Catalyzed Carbene Reactions Toward C–H Insertion and Cyclopropanation. Restricted; Files Only

Abstract

Abstract

Expanding The Scope of Reactions and Applications for Dirhodium(II) Tetracarboxylate Catalyzed Carbene Reactions Toward C–H Insertion and Cyclopropanation.

By Yasir Naeem

The utilization of rhodium carbenes in catalyst-directed C–H functionalization, specifically in C–H insertion chemistry, has emerged as a potent synthetic method. A crucial advancement in this field entails harnessing the synergy between donor/acceptor carbenes and chiral dirhodium tetracarboxylate catalysts. The primary objective of the research detailed in this thesis is to employ our advanced next-generation chiral dirhodium catalysts for the attainment of highly site- and stereoselective C–H functionalization reactions mediated by donor/acceptor carbenes. This thesis is structured into four chapters. The first chapter provides an overview of general knowledge on dirhodium tetracarboxylate catalysts, focusing on selective carbene chemistry in C–H functionalization.

The second chapter focuses on catalyst-controlled C−H functionalization using donor/acceptor carbenes, highlighting its efficiency in achieving high levels of site and stereoselectivity. This research extends the scope of donor/acceptor carbene C−H functionalization to systems where the acceptor group is phosphonate. The sterically demanding phosphonate group resulted in significantly higher selectivity for primary sites over more crowded positions compared to the previously studied carboxylate ester group. The methodology's effectiveness was demonstrated by the late-stage primary C−H functionalization of estrone, adapalene, (S)-naproxen, clofibrate, and gemfibrozil derivatives.

The third chapter explores C−H functionalization chemistry for modifying triarylamine derivatives with carboxylic esters and norbornene, which are important for materials applications. Specifically, various triarylamines and 4,4′-bis(diarylamino)biphenyl were subjected to C(sp2)–H functionalization using a diazoacetate bearing a protected carboxylic acid functional group, in the presence of a dirhodium tetracarboxylate catalyst. This approach potentially provides straightforward access to a diverse array of Hole-Transport Materials (HTMs) with different functional groups.

The fourth and the final chapter of the thesis is focused on developing a novel approach for synthesizing aryl and heteroaryl diazo phosphonates using a palladium-catalyzed cross-coupling reaction. This method relies on readily available aryl iodides as starting materials, therefore avoiding the need for the hazardous diazo transfer reagent, 4-Acetamidobenzenesulfonyl azide, which is commonly used in traditional diazo transfer reactions to create different diazo phosphonate compounds. As a result, this approach enables the rapid and efficient creation of a diverse library of valuable diazo phosphonate compounds. The diazo phosphonate compounds synthesized in this thesis were subsequently subjected to cyclopropanation reactions using our next-generation dirhodium tetracarboxylate catalyst. 

Table of Contents

Table of Contents

Chapter 1. Introduction of Donor/acceptor Carbene and Dirhodium Tetracarboxylate Catalysts Chemistry..........................................................................................1

1.1 Introduction..................................................................................1 1.2 Conclusions.................................................................................17

Chapter 2. Enantioselective Intermolecular C−H Functionalization of PrimaryBenzylic C−H Bonds Using ((Aryl)(diazo)methyl)phosphonates.............................................18

2.1 Introduction................................................................................18 2.2 Conclusion..................................................................................49

Chapter 3. Dirhodium C−H Functionalization of Hole-Transport Materials..................50

3.1 Introduction................................................................................50 3.2 Conclusion..................................................................................67

Chapter 4. Synthesis of aryl- and hetroaryl diazophosphonates by palladium-catalyzed cross-coupling reactions and cyclopropanation......................................................69

4.1 Introduction................................................................................69 4.2 Conclusions.................................................................................90

References....................................................................................................91 

About this Honors Thesis

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School	Laney Graduate School
Department	Chemistry
Degree	Ph.D.
Submission	Honors Thesis
Language	English
Research Field	Chemistry, Organic
关键词	Donor/acceptor carbenes, C−H functionalization, diazophosphonates, chiral catalyst, dirhodium tetracarboxylate, cross-coupling, cyclopropanation, rhodium carbene, asymmetric catalysis.
Committee Chair / Thesis Advisor	Huw M.L. Davies, Emory University
Committee Members	Bill Wuest, Emory University Frank McDonald, Emory University

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