Cu- and Pd-Catalyzed a-Hydroxycyclopropanol Ring Opening Reactions: Electrophilic Trappings to 3-Furanones, and Carbonylation to 4-Ketovalerolactones. Open Access

Abstract

Cyclopropanols are a useful tool in synthetic organic chemistry, due to their intrinsic ring strain within the cyclopropane ring. For cyclopropanols, they can undergo two distinct reactivity modes. One of which is heterolytic cleavage to form a metal-homoenolate species, and the other being a b-keto radical species. Both reactive intermediates have interesting reactivity, and both can be formed selectively by careful choice of the reaction conditions applied. Hydroxycyclopropanols have been studied in recent years to access various useful synthetic motifs that are present in different natural products, and medicinally relevant compounds. The Dai group has been a pioneer in this area chemistry, synthesizing an array of scaffolds from these hydroxycyclopropanols. The Dai group managed to synthesize these scaffolds from the generated metal-homoenolate species with or without the presence of carbon monoxide to synthesize oxaspirolactones, THF and THP-fused bicyclic lactones, and substituted THF and THP heterocycles. Herein, the application of similar concepts to access two new classes of scaffolds, 3-furanones, and 4-ketovalerolactones will be discussed. Notably these two scaffolds can be accessed from the same starting material, where careful reaction optimization will be disclosed for each method. Additionally, the substrate scope for each method, diversification, and mechanistic studies will be discussed.

Table of Contents

LIST OF TABLES: i

LIST OF SCHEMES: ii

LIST OF ABBREVIATIONS: iii

CHAPTER 1. Cu- and Pd-catalyzed a-hydroxycyclopropanol ring opening reactions: electrophilic trappings to 3-furanones, and carbonylation to 4-ketovalerolactones. 1

1.1 Introduction: 1

1.2 Results and Discussion: 7

1.3 Conclusions: 27

1.4 Experimental Data 27

1.4.1 General Methods: 27

1.4.2 Representative procedure 1 for the synthesis of a-hydroxycyclopropanols: 28

1.4.3 Representative procedure 2 for the synthesis of a-hydroxycyclopropanols: 29

1.4.4 Representative procedure for copper-catalyzed ring opening intramolecular trapping reaction: 40

1.4.5 Representative procedure for palladium-catalyzed carbonylative lactonization reaction: 52

References: 63

About this Master's Thesis

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School	Laney Graduate School
Department	Chemistry
Degree	M.S.
Submission	Master's Thesis
Language	English
Research Field	Chemistry, Organic
Keyword	Palladium Carbonylation Catalysis Copper Cyclopropanol
Committee Chair / Thesis Advisor	Dai, Mingji, Emory University
Committee Members	Davies, Huw, Emory University Wuest, Bill, Emory University

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