臺灣博碩士論文加值系統

Developments of three new methods for fullerene functionalization through transition metal catalysis are presented.
Palladium-catalyzed heteroannulation of [60]fullerene with N-substituted benzamides, which proceeds through direct sp2 C–H bond activation to form 7-membered ring pallada-intermediate with C60, led to formation of [60]fulleroisoquinolinones in moderate to good yields 8–64% based on recovered C60. C–H bond activation is highly regioselective in this reaction.
An efficient palladium-catalyzed chelating-group-assisted C−H activation of N-sulfonyl-2-aminobiaryls and their annulations with [60]fullerene via sequential C–C and C–N bond formation at room temperature to afford [60]fulleroazepines is demonstrated for the first time. The formation [60]fulleroazepines is highly regioselective and tolerance to both electron-withdrawing and electron-donating groups on the aryl moiety with good monofuctionalized fullerene reaction yield (up to 51% isolated yield and 85% based on recovered C60).
A system with ingredients of late transition-metal halides, phosphines, water and reducing agent in 1,2-dichlorobenzene can efficiently catalyze the intermolecular reductive coupling of [60]fullerene with N-sulfonylaldimines to afford novel 1,2-hydrobenzylated [60]fullerene derivatives. A control experiment in the absence of aldimines produced C60H2, which proved that the reaction could proceed via a [60]fullerene metal complex, M(η2-C60)(ligand). An isotope labeling experiment with D2O as deuterio source resulted in deuteriobenzylation with deterium bonded to the sp3-carbon of C60, providing evidence of a five-membered azametallacycle intermediate. Evaluation of the scope of reductive coupling reaction with versatile aldimines gave access to the novel hydrobenzylated products. All the reductive coupling products were completely characterized by infrared and NMR spectroscopy and ESI-mass spectrometry. Based on these results, a possible reaction mechanism is proposed.
Synthesized series of open-cage fullerene derivatives possessing with N-alkylmaleimide moiety as n-type materials for organic solar cells.

Developments of three new methods for fullerene functionalization through transition metal catalysis are presented.
Palladium-catalyzed heteroannulation of [60]fullerene with N-substituted benzamides, which proceeds through direct sp2 C–H bond activation to form 7-membered ring pallada-intermediate with C60, led to formation of [60]fulleroisoquinolinones in moderate to good yields 8–64% based on recovered C60. C–H bond activation is highly regioselective in this reaction.
An efficient palladium-catalyzed chelating-group-assisted C−H activation of N-sulfonyl-2-aminobiaryls and their annulations with [60]fullerene via sequential C–C and C–N bond formation at room temperature to afford [60]fulleroazepines is demonstrated for the first time. The formation [60]fulleroazepines is highly regioselective and tolerance to both electron-withdrawing and electron-donating groups on the aryl moiety with good monofuctionalized fullerene reaction yield (up to 51% isolated yield and 85% based on recovered C60).
A system with ingredients of late transition-metal halides, phosphines, water and reducing agent in 1,2-dichlorobenzene can efficiently catalyze the intermolecular reductive coupling of [60]fullerene with N-sulfonylaldimines to afford novel 1,2-hydrobenzylated [60]fullerene derivatives. A control experiment in the absence of aldimines produced C60H2, which proved that the reaction could proceed via a [60]fullerene metal complex, M(η2-C60)(ligand). An isotope labeling experiment with D2O as deuterio source resulted in deuteriobenzylation with deterium bonded to the sp3-carbon of C60, providing evidence of a five-membered azametallacycle intermediate. Evaluation of the scope of reductive coupling reaction with versatile aldimines gave access to the novel hydrobenzylated products. All the reductive coupling products were completely characterized by infrared and NMR spectroscopy and ESI-mass spectrometry. Based on these results, a possible reaction mechanism is proposed.
Synthesized series of open-cage fullerene derivatives possessing with N-alkylmaleimide moiety as n-type materials for organic solar cells.

Table of Contents
Chapter 1 1
Introduction 1
Discovery of the fullerene 1
1.2 Solubility of C60 fullerene 2
1.3 Characterizations of the fullerene 3
1.4 General reactivity of C60 fullerene 5
1.4.1 Cycloaddition Reactions 5
1.4.2 [4+2] Cycloaddition Reactions 5
1.4.3 [3+2] Cycloaddition Reaction 6
1.4.4 [2+2] Cycloaddition Reaction 7
1.4.5 [2+1] Cycloaddition Reaction 8
1.5 Transition metal complexes of C60 fullerene 9
1.5.1 Iridium Complexes 10
1.5.2 Rhodium and Zirconium complexes14b 11
1.6 Nucleophilic reactions 12
Hydroalkylation and hydroarylation reaction 12
1.6.1 Bingel reaction 13
1.7 Radial reactions 13
1.7.1 Reaction of C60 with nitriles 13
1.7.2 Reactions with ketones 14
1.7.3 Reactions with ethers 15
Recent literature work on transition metal catalyzed functionalization on [60]fullerene 16
1.8.1 Palladium catalyzed reactions 16
1.8.2 Rhodium mediated reaction 18
1.8.3 Cobalt mediated reactions 19
1.9 Applications of fullerene derivatives 20
1.9.1 Biological applications 20
1.9.2 Applications in material sciences 21
PCBM derivatives and ICBA 21
1.9.3 Fulleroisoquinolinones 22
1.10 Ortho C–H bond activation and functionalization in organic synthesis 23
1.10.1 Different directing groups 23
1.10.2 Amide directing group 24
1.10.3 Carbonyl directing group 24
1.10.4 Carboxylic acid directing group 25
1.10.5 Oxime ether as directing group 26
1.10.6 Imine directing group 26
1.10.7 Anilide as a directing group 26
1.11 References 34
Chapter 2 38
2.1 Introduction 39
2.1.1 Rhodium mediated alkyne insertion of benzamides 39
2.1.2 Ruthenium mediated alkyne insertion 40
2.1.3 Arylation and cyclization 41
2.1.4 Ortho Olefination of Benzamides 42
2.1.5 Carbonyl insertion 43
2.2 Annulation of Benzamides with [60]Fullerene through Palladium(II)-Catalyzed C–H Bond Activation 44
2.2.1 Results and discussion 45
2.3 Characterization of fulleroisoquinolinones 54
2.4 Proposed mechanism for the formation of fulleroisoquinolinones 59
2.5 Electrochemical properties of different fullerene fused heterocyclic compounds 60
2.6 Mechanism for the formation of fulleroindoles 65
2.7 Crystallographic data of compound 2l. 66
2.8 Conclusion 71
2.9 General methods 72
2.10 Experimental section 73
2.11 References 88
Chapter 3 89
3.1 Introduction 90
3.2 The importance of 2-aminobiaryls in organic synthesis 91
3.2.1 Synthesis of phenanthridine derivatives 92
3.2.2 Synthesis of carbazoles 93
3.3 Azepine synthesis in small molecules 95
3.4 Palladium-Catalyzed and Hybrid Acids-Assisted Synthesis of [60]Fulleroazepines in One Pot Under Mild Conditions: Annulation of N-sulfonyl-2-aminobiaryls with [60]Fullerene through Sequential C–H Bond Activation, C–C and C–N Bond Formation 97
3.5 Retrosynthetic analysis 99
3.6 Optimization studies for the synthesis of [60]Fulleroazepines 100
3.7 Study of the reaction scope 102
3.8 Characterization of fulleroazepine 109
3.9 Mechanistic considerations for the formation of [60]fulleroazepines 114
3.10 Electeochemical studies of [60]fulleroazepine derivatives 115
3.11Conclusion 117
3.13 Experimental section 119
3.13 References 161
Chapter 4 162
4. Introduction 164
4.1 Nickel catalyzed Reductive coupling reactions 164
4.1.1 Alkyne/ imine coupling reactions 165
4.1.2Alkyne/ aldehyde coupling reactions 166
4.1.3 Alkene/ imine coupling reactions 166
4.2 Nickel catalyzed reaction of C60 167
4.3 Co-catalyzed hydroalkylation of C60 169
4.4 Evolution of Late Transition-Metal-Catalyzed Intermolecular Reductive Coupling Reaction of [60]Fullerene and N-sulfonylaldimines: Competing Formation of Hydrobenzylated [60]Fullerenes and 1,2-Dihydrofullerene 170
4.5 Optimization studies for Reductive Coupling of [60]Fullerene and N-Sulfonyl Aldimines 172
4.6 Reaction scope studies 177
4.7 Mechanistic evidence 181
4.8 Deuterium labeling experiment 182
4.9 Mechanistic consideration 185
4.10 Characterization of hydrobenzylated fullerene derivatives 187
4.11 Conclusion 191
4.12 Experimental section 192
4.12.1 Synthetic procedures for the catalysts 192
4.12.1.1 Synthesis of [Cp*RhCl2]2 192
4.12.1.2 Synthesis of [Cp*IrCl2]2 192
4.12.1.3 Bis(triphenylphosphine)palladium(II) dichloride 193
4.12.1.4 Synthetic procedure for nickel complexes 193
4.12.1.5 Synthesis of NiBr2(P(p-tolyl)3)2 193
4.12.1.6 Synthetic procedure for NiBr2[phen] 194
4.12.1.7 Synthetic procedure for NiBr2(PPh3)2 194
4.12.1.8 Synthetic procedure for NiBr2(dppe) 194
4.12.1.9 Synthetic procedure for CoI2(PPh3)2 195
4.14 References 217
Chapter 5 221
Synthesis of Open-Cage Fullerene Derivatives Possessing with Maleimide and Solubilizing Alkyl Functionality 221
5.1 Introduction 221
5.2 Results and discussion 227
5.3 Electeochemical property studies of open cage fullerene derivatives 11-15 229
5.4 Characterization of open-cage fullerene derivatives 233
5.5 Conclusion 233
5.6 Experimental section 234
5.7 References 266

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