Palladium-catalyzed cross-coupling reaction of diazoles and activated alkenes for the synthesis of alkenyl heteroarenes = 팔라듐 촉매 조건에서 활성화된 알켄과 다이아졸의 교차 짝지음 반응을 통한 알케닐 헤테로아렌의 합성

다국어 초록 (Multilingual Abstract)

In chapter 1, the synthesis of alkenyl imidazoles was described. Few examples were reported for the regioselective alkenylation of the C5-position of imidazoles without a pre-functional group or a directing group. Thus, this work focused on the reactivity based on electronic properties of imidazoles for the regioselective C−H alkenylation. It was successful to synthesize C5-alkenylated imidazoles from C2-unsubstituted imidazoles and C2-substituted ones. Mechanistic studies which contain kinetic isotope effect experiments and deuterium exchange experiments explained the reactivity of imidazoles. For its application, 5, 6-disubstituted benzimidazoles were synthesized through the SEM-group switch, secondary alkenylation, and electrocyclization.
Chapter 2 focused on the synthesis of diheteroaryl alkenes. There was few example of introducing two different heterocycles to bicyclic alkenes. This chapter described three-component coupling reactions using haloheteroarenes, norbornadiene, and heteroarenes. Then, desired diheteroaryl alkenes were synthesized through the retro-Diels-Alder reaction. A variety of halopyrazoles and 1, 3-azoles were examined, giving the corresponding three-component coupling products.

목차 (Table of Contents)

• Contents
• Chapter 1. Palladium-Catalyzed Regioselective Alkenylation of Imidazoles and its Application for the Synthesis of Unsymmetrically Substituted Benzimidazoles
• 1. Introduction 1
• 2. Results and Discussion 4
• 3. Conclusion 15
• 4. Experimental Section 16
• 4.1. General Information 16
• 4.2. Experimental Procedures 16
• 4.3. Product Characterization Data 18
• 4.4. 1H NMR and 13C NMR Spectra 29
• 4.5. X-ray Crystal Data 43
• 5. References 52
• Chapter 2. Synthesis of Diheteroaryl Alkenes by Sequential Three-Component Coupling Reaction and Retro-Diels-Alder Reaction
• 1. Introduction 54
• 2. Results and Discussion 56
• 3. Conclusion 62
• 4. Experimental Section 63
• 4.1. General Information 63
• 4.2. Experimental Procedures 63
• 4.3. Product Characterization Data 64
• 4.4. 1H NMR and 13C NMR Spectra 68
• 5. References 72