I. Selective Chlorination and Fluorination of Quinols II. Synthetic Study of Strongylophorine-26

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I. Selective Chlorination and Fluorination of Quinols II. Synthetic
Study of Strongylophorine-26, Is A Well-Researched Topic, It Is To Be Used As A Guide Or Framework For Your Research.

Abstract

Organic compounds containing halogen are an important and useful class of intermediates that can be converted to other functionalities. This thesis describes our strategy in selective chlorination and fluorination of quinols to offer the corresponding aromatic structures. Quinols,
or cyclohexadienones, as oxidized derivatives of phenols, have their remarkable chemical reactivities, including additions to enone, enolate alkylations, aldol reactions, cycloadditions, and rearrangements. Dienone-phenol rearrangement provides the asymmetric route since the
stereocenters located in the six-membered ring of various cyclohexanone were widely using in building larger chiral arrays for many total synthesis chapters one of this thesis discusses our new selective nucleophilic chlorination of quinol to afford ortho- chloride phenol. This one-step selective chlorination can easily be performed using readily available quinols and thionyl chloride. In Chapter two, inspired by chlorination strategy, we develop a new fluorination strategy to offer fluorinated cyclohexadiene products by deoxofluorination of quinols. Chapter three describes our study work on the total synthesis of
Strongylophorine-26. The difficulties we met and our solution is discussed.

TABLE OF CONTENTS

ABSTRACT……………………………………………………………………………………………………….. iv
ACKNOWLEDGMENTS……………………………………………………………………………………… v
TABLE OF CONTENTS…………………………………………………………………………………….. vii
LIST OF FIGURES………………………………………………………………………………………………. x
LIST OF TABLES………………………………………………………………………………………………..xi
LIST OF SCHEMES…………………………………………………………………………………………… xii
STANDARD ABBREVIATIONS AND ACRONYMS…………………………………………..xiii
CHAPTER 1 Selective Synthesis of ortho-Chlorophenol by Quinol Nucleophilic Addition 1
1.1 Selective Synthesis of ortho-Chlorophenol by Quinol Nucleophilic Addition…………. 1
1.1.1 Halogenation of Phenol………………………………………………………………………………….1
1.1.2 Green Chemistry in the Chlorination Phenols………………………………………………….. 2
1.1.3 Yin’s Nucleophilic Selective Chlorination of Quinone Monoketals……………………… 5
1.2 Selective Chlorination of Quinol to Form o-Chlorophenol with Thionyl Chloride in the
Presence of Base…………………………………………………………………………………………………… 9
1.2.1 Chlorination of Quinol by Thionyl Chloride…………………………………………………….. 9
1.2.2 Mechanism of Regioselective Chlorination…………………………………………………….. 18
1.2.3 Summary……………………………………………………………………………………………………. 20
References…………………………………………………………………………………………………………..21
Experimental and Supporting Information……………………………………………………………… 24

CHAPTER 2 Deoxofluorination between Diethylaminousulfur Trifluoride (DAST) and
Quinol………………………………………………………………………………………………………………..69
2.1 Fluorine Chemistry from Past to Now on…………………………………………………………..69
2.1.1 Fluorine Chemistry from the 19th Century to Modern Time……………………………….69
2.1.2 Typical Organofluorine Compounds……………………………………………………………… 71
2.1.3 Interaction of C-F Bonds……………………………………………………………………………… 75
References…………………………………………………………………………………………………………..78
2.2 Fluorination of Quinol……………………………………………………………………………………. 81
2.2.1 Synthesis of Complex Organofluorine Compounds…………………………………………..81
2.2.2 Fluorination of Quinol………………………………………………………………………………..82
2.2.3 Deoxofluorination in Quinol………………………………………………………………………….84
2.2.4 Experimental Scope of Quinols with DAST…………………………………………………….. 85
2.2.5 Mechanism of DAST in Fluorination of Quinol………………………………………………. 92
2.2.6 Conclusion…………………………………………………………………………………………………. 94
References…………………………………………………………………………………………………………..95
Experimental and Supporting Information……………………………………………………………… 96
CHAPTER 3 Study of Total Synthesis of Anticancer Agent Strongylophorine-26 177
3.1 Introduction of Strongylophorine Family……………………………………………………….177
3.2 Synthesis of Strongylophorine………………………………………………………………………..179
3.2.1 Professor Poulsen Strategy toward Strongylophorine-2………………………………….179
3.2.2 Synthesis of Strongylophorine-26 by Catalytic Oxidative Quinone Method………. 181
3.2.3 Dethe and Sau’s Strategy toward Strongylophorine-2 and 9……………………………183

3.3 Study of Total Synthesis of Anticancer Agent Strongylophorine-26……………………187
3.3.1 Brief Route to Strongylophorine-26………………………………………………………………187
3.3.2 Synthesis of Precursor 3.28 from Farnesol 3.34……………………………………………. 188
3.3.3 The Study of Sharpless Oxidation…………………………………………………………………190
3.3.4 Conclusion……………………………………………………………………………………………….. 194
References…………………………………………………………………………………………………………196
Experimental and Supporting Information……………………………………………………………. 200

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YourPastQuestions Brand

Additional information

Author

Sihan Li

No of Chapters

3

No of Pages

234

Reference

YES

Format

PDF

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