Metal Catalyst Methodology Development towards Carbon-Oxygen Bond Formation: Synthesis of Vinyl Ethers and Vinyl Esters Público

Abstract

Vinyl ethers and vinyl esters are versatile functional groups utilized in synthetic and bioorthogonal applications, and they are found in natural products with medicinal properties. Novel scorpionate Ru complexes were synthesized for vinyl ether synthesis, however they are unable to promote reactivity with alcohols. The novel scorpionate catalyst were applied towards vinyl ester synthesis, and a reactive system with tunable stereoselectivity depending on ligands of choice is described. Deuterium experiments were conducted, suggesting an alternative pathway for vinyl ester synthesis besides vinylidene formation. Finally, Chan-Lam coupling reactions were optimized and applied towards complex glycoside vinyl ether synthesis. Screening Chan-Lam reaction conditions provided insight into the obstacles preventing Chan-Lam from being a robust method for vinyl ether synthesis. 

Table of Contents

Chapter 1: Ru Catalyst development towards complex vinyl ether synthesis

1.1 Introduction and Background…………………………………………………………..1

1.1.1      Vinyl Ether……………………………………………...……………….1

1.1.2      Vinyl Ester………………………………..……………………………..7

1.2 Synthetic Strategy………………………………………………………………………8

1.3 Catalyst Synthesis and Results…………………………………………...……………10

1.3.1      Preliminary Catalyst Synthesis (Synthesis of HB(Pz)3Ru(L)Cl)…….…10

1.3.2      Hydrogen Bonding Accepting Catalyst Synthesis (Synthesis of HB(BzTz)3Ru(L)Cl)………………………………………..………….14

1.3.3      Electron Deficient Metal Catalyst Synthesis…………….……………..17

1.3.4      Hydroalkoxylation Experiments………………………………...……..20

1.4 Conclusions…………………………………………………...………………………22

1.5 Experimental Section……………………………………………………………….....23

1.6 References………………………………………………………………………...…..31

Chapter 2: Ligand and Substrate Effects on Regio- and Stereoselectivity of Carboxylic Acids and Terminal Alkyne Addition Catalyzed by Ruthenium(II) Complexes Towards Vinyl Ester Synthesis

2 2.1 Introduction…………………………………………………………………...………38

2.2 Background……………………………………………………………………..…….42

2.3 Results and Discussion…………………………………………………………….….45

2.3.1      Catalyst and Ligand Screening…………………………………………45

2.3.2      Substrate Expansion……………………………………………………48

2.3.3      Deuterium Experiments………………………………………….…….50

2.4 Conclusions…………………………………………………………………………...56

2.5 Experimental Section……………………………………………………………….....58

2.6 References………………………………………………………………………….…76

Chapter 3: Optimizing Chan-Lam coupling for vinyl ether synthesis

3.1      Introduction………….………………………………………………...……………80

3.2      Synthetic Strategy…………………..……………………………………………….87

3.3      Results and Discussion………………………………………..…………………….91

3.3.1      Sugar Synthesis……………………………………...…………..……..91

3.3.2      Cu(II)(OAc)2 Optimization………………………………….…………93

3.3.3      Other Cu Catalyst Screening……………………………….…………..98

3.2      Conclusions………………..………………………………………………………101

3.3      Experimental Section………………………...………………………………….....103

3.4      References……………………………………………..…………………………..111

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School	Laney Graduate School
Department	Chemistry
Degree	Ph.D.
Submission	Dissertation
Language	English
Research Field	Chemistry, Organic
Palavra-chave	Vinyl ester vinylidene Catalyst Vinyl ether Methodology
Committee Chair / Thesis Advisor	Frank McDonald, Emory University
Committee Members	Simon Blakey, Emory University Mingji Dai, Emory University

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