光催化的有氧氧化反應是一種新穎且綠色的合成策略。本研究利用氧化亞銅 奈米晶體作為光催化劑，用於苯基硼酸羥基化反應。在控制實驗中可知光源、氧 氣及電子供體對於反應的重要性，並且水為最佳的溶劑，乙基二異丙基胺 (DIPEA)為最佳的電洞受體，在最佳條件下探討催化劑。當用具不同晶面的氧化 亞銅立方體、八面體以及菱形十二面體奈米晶體為催化劑，結果具{110}面的菱 形十二面體氧化亞銅奈米晶體的催化效果為最好，產率可達 95%。我們也將該實 驗條件用於帶不同官能團的芳基硼酸以進行羥基化，發現不同官能團通常都可得 到不錯的產率。最後根據自由基捕捉實驗以及 EPR 實驗提出一個可能的機制。

Photocatalytic aerobic oxidation is a novel and green synthetic strategy. In this study, Cu2O nanocrystals were used as photocatalysts for the hydroxylation of phenylboronic acids. The importance of light source, oxygen and hole acceptor has been established in the control experiments. The catalytic activities of {100}-bound Cu2O cubes, {111}-enclosed octahedra, and {110}-terminated rhombic dodecahedra have been investigated using the best reaction conditions with water as the best solvent and diisopropylethylamine (DIPEA) as the best hole acceptor. Rhombic dodecahedra showed the best catalytic performance with 95% yield. Hydroxylation of aryl boronic acids with different functional groups were also explored, showing good to excellent product yields. A possible mechanism has been proposed based on radical trapping experiments and EPR experiment

論文摘要.....I
Abstract.....II
Acknowledgement.....III
List of Figures.....VI
List of Table.....VIII
List of Schemes.....IX
List of Spectrum.....X
1.Introduction.....1
1.1Cuprous Oxide and Facet Effects.....1
1.2Application of cuprous oxide in organic chemistry.....4
1.3 Phenols and phenol synthesis.....7
1.4 Photocatalytic hydroxylation of aryl boronic acid.....9
1.4.1 Transition metal complex photocatalyst.....9
1.4.2 Organic photocatalyst.....11
1.4.3 Covalent organic frameworks as photocatalysts.....12
1.4.4 Metal-organic frameworks photocatalyst.....14
1.4.5 Metal complex-linked porous organic polymers.....15
2. Motivation.....18
3. Experiment Section.....19
3.1 Instrumentation.....19
3.2 Chemicals.....20
3.3 Synthesis of polyhedral Cu2O nanocrystals.....21
3.4 Calculations of particle weights for photocatalytic performance comparison.....23
3.5 Cu2O nanocrystal-photocatalyzed hydroxylation of arylboronic acids .....25
3.6 Photocatalytic activity comparison experiment.....26
3.7 Free radical trapping experiment.....27
3.8 Electron paramagnetic resonance experiment.....28
4. Results and Discussion.....30
4.1 The shapes and sizes of Cu2O nanocrystals.....30
4.2 Photocatalytic hydroxylation of arylboronic acid.....33
4.3 Mechanism study.....44
4.4 Proposed mechanism.....47
5. Conclusion.....48
6. Spectroscopic Data of Isolated Products.....49
7. References..... 52

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