Visible Light Photocatalyzed Redox-Neutral Organic Reactions and Synthesis of Novel Metal-Organic Frameworks

Photocatalyzed Redox-Neutral
 
Author:
Basudev Sahoo
Release at: 2017
Pages: 274
Edition:
First Edition
File Size: 12 MB
File Type: pdf
Language: English


Content of Visible Light Photocatalyzed Redox-Neutral Organic Reactions and Synthesis of Novel Metal-Organic Frameworks



1 Introduction to Photocatalysis ............................... 1

1.1 Historical Background .................................. 1

1.2 Classifications of Photocatalyst............................ 2

1.3 Characteristics of Homogeneous Photocatalysts ............... 3

1.4 Visible Light Photocatalysis in Organic Synthesis ............. 5

1.4.1 Photoredox Catalyzed Organic Transformations via Electron Transfer.............................. 5

1.4.2 Photocatalyzed Organic Transformations via Triplet Energy Transfer ................................. 18

1.5 Summary ............................................ 19

References................................................ 20

2 Dual Gold and Visible Light Photoredox-Catalyzed Heteroarylations of Non-activated Alkenes ..................... 25

2.1 Introduction .......................................... 25

2.1.1 General Properties of Homogeneous Gold Catalysts ...... 25

2.1.2 Gold-Catalyzed Organic Transformations .............. 27

2.1.3 Aryldiazonium Salts: Synthesis and Reactivity .......... 35

2.1.4 Diaryliodonium Salts: Synthesis and Reactivity ......... 36

2.2 Results and Discussion .................................. 37

2.2.1 Inspiration ...................................... 37

2.2.2 Intramolecular Oxy- and Aminoarylation of Alkenes ..... 39

2.2.3 Intermolecular Oxyarylation of Alkenes ............... 44

2.2.4 Mechanistic Studies on Heteroarylations of Alkenes...... 49

2.3 Summary ............................................ 54

References................................................ 54

3 Visible Light Photoredox Catalyzed Trifluoromethylation-Ring Expansion via Semipinacol Rearrangement..................... 59

3.1 Introduction .......................................... 59

3.1.1 General Features of Fluorinated Compounds............ 59

3.1.2 Importances of Fluorinated Compounds ............... 59

3.1.3 Radical-Polar Crossover Process ..................... 61

3.1.4 Trifluoromethylation of Alkenes ..................... 61

3.1.5 Semipinacol Rearrangements........................ 67

3.2 Results and Discussion .................................. 69

3.2.1 Inspiration ...................................... 69

3.2.2 Preliminary Experiments and Optimization Studies....... 70

3.2.3 Substrate Scope and Limitations ..................... 72

3.2.4 Follow up Transformations of Products ............... 75

3.2.5 Mechanistic Studies............................... 76

3.3 Summary ............................................ 78

References................................................ 79

4 Transition Metal Free Visible Light-Mediated Synthesis of Polycyclic Indolizines .................................... 81

4.1 Introduction .......................................... 81

4.1.1 General Properties of Indolizines .................... 81

4.1.2 Importances of Indolizines ......................... 82

4.1.3 Synthesis of Indolizines ........................... 82

4.1.4 Functionalization of Indolizines via Transition Metal Catalysis ....................................... 87

4.2 Results and Discussion .................................. 89

4.2.1 Inspiration ...................................... 89

4.2.2 Reaction Design ................................. 90

4.2.3 Preliminary Experiments and Optimization Studies....... 90

4.2.4 Scope and Limitations............................. 93

4.2.5 Structural Manipulations of the Indolizine Product ....... 97

4.2.6 Mechanistic Investigations ......................... 98

4.3 Summary ............................................ 103

References................................................ 105

5 Synthesis and Characterizations of Novel Metal-Organic Frameworks (MOFs)....................................... 109

5.1 Intoduction ........................................... 109

5.1.1 Historical Background............................. 109

5.1.2 General Characteristic Features of Metal-Organic Frameworks (MOFs).............................. 109

5.1.3 Applications of Metal-Organic Frameworks (MOFs)...... 112

5.1.4 Synthesis of Metal-Organic Frameworks (MOFs) ........ 113

5.2 Results and Discussion .................................. 116

5.2.1 Inspiration ...................................... 116

5.2.2 Synthesis of Novel Metal-Organic Frameworks (MOFs).............................. 116

5.2.3 Structural Analysis of Novel Metal-Organic Frameworks (MOFs) ........................................ 118

5.2.4 Dye Absorption Studies of Novel Metal-Organic Frameworks (MOFs).............................. 122

5.2.5 Photophysical Studies of Novel Metal-Organic Frameworks (MOFs).............................. 123

5.3 Summary ............................................ 124

References................................................ 125

6 Experimental Section ...................................... 127

6.1 General Considerations.................................. 127

6.2 Synthesis of Photocatalysts............................... 133

6.3 Oxy- and Aminoarylations of Alkenes ...................... 138

6.3.1 Synthesis of Gold Catalysts......................... 138

6.3.2 Synthesis of Alkene Substrates ...................... 139

6.3.3 Synthesis of Aryldiazonium Salts .................... 145

6.3.4 Synthesis of Diaryliodonium Salts ................... 145

6.3.5 Synthesis and Characterization of Oxy- and Aminoarylated Products ................. 146

6.4 Visible Light Photoredox Catalyzed Trifluoromethylation-Ring Expansion via Semipinacol Rearrangement .................. 163

6.4.1 Synthesis of (Oxa)Cycloalkanol Substrates ............. 163

6.4.2 Synthesis and Characterization of Trifluoromethylated Cycloalkanone Compounds......................... 175

6.4.3 Synthetic Manipulations of Trifluoromethylated Cycloalkanone Product ............................ 187

6.4.4 Mechanistic Investigations ......................... 190

6.5 Transition Metal Free Visible Light Mediated Synthesis of Polycyclic Indolizines ................................ 195

6.5.1 Synthesis of Substrates ............................ 195

6.5.2 Photocatalytic Synthesis of Indolizines ................ 220

6.5.3 Structural Manipulations of Indolizine ................ 235

6.5.4 Mechanistic Experiments........................... 237

6.6 Synthesis and Characterizations of Novel Metal-Organic Frameworks (MOFs).................................... 244

6.6.1 Synthesis of 4,4′,4′′-Boranetriyltris(3,5-Dimethylbenzoic Acid) (H3TPB) .................................. 245

6.6.2 Synthesis of (S)-2-(4-Benzyl-2-Oxooxazolidin-3-yl) Terephthalic Acid ................................ 247

6.6.3 Synthesis of DUT-6 (Boron) (234) ................... 248

6.6.4 Synthesis of Chiral DUT-6 (Boron) (235).............. 249

6.6.5 Single Crystal X-Ray Analysis of DUT-6 (Boron) ....... 249

6.6.6 Determination of BET Area ........................ 250

6.6.7 CO2 Physisorption Isotherms for DUT-6............... 250

References................................................ 251

Curriculum Vitae ............................................ 255

GET THIS BOOK
Categories:
Similar Books

0 comments: