一价铜催化Ullmann 反应合成联苯醚和芳基烷基醚的研究

联苯醚和芳基烷基醚类化合物是天然产物和聚合物材料中的重要的片段结构，研究其合成具有重要意义。近年来，过渡金属催化形成碳-氧键已成为制备联苯醚和芳基烷基醚类化合物的重要方法。钯体系虽然成功，但由于其属于贵金属，价格昂贵，而且反应所必须的有机膦配体，毒性较大，对环境危害较大，所以其应用受到了限制。 本论文通过利用空气稳定的Cu(bpy)2BF4 配合物，使得苯酚和烷基醇有效地进行偶合得到联苯醚产物。该方法可以在不使用昂贵弱碱Cs2CO3 的情况下，取得很好的产率，并且在较低的催化剂载入量的情况下，可以很好地适应各种官能团取代的底物。 本论文通过配体的扫描筛选，使得溴代苯和烷基醇的偶合反应得到了发展。更重要的是，使用该体系时分子间和分子内的碳-氧键都可以形成。通过该方法合成了一系列苯并环醚类化合物，这也是一价铜体系催化制备该类化合物的首次报道。

An Efficient Ullmann-Type C-O Bond Formation Catalyzed by an Air-Stable Copper(I)-Bipyridyl Complex

An efficient O-arylation of phenols and aliphatic alcohols with aryl halides was developed that uses an air-stable copper(I) complex as the catalyst. This arylation reaction can be performed in good yield in the absence of Cs2CO3. A variety of functional groups are compatible with these reaction conditions with low catalyst loading levels.

Facile synthesis of 9,10-diarylphenanthrenes and poly(9,10-diarylphenanthrene)s

One-pot reduction of 9,10-diaryl-9,10-dihydrophenanthrene-9,10-diols to 9,10-diarylphenanthrenes was achieved with Zn/H+ in acetic acid. Accordingly, various novel phenanthrenes and polyphenanthrenes with efficient blue emission were easily synthesized.

Electronic structures and chemical bonding in diatomic ScX to ZnX (X = S, Se, Te)

Bond distances, vibrational frequencies, electron affinities, ionization potentials, dissociation energies, and dipole moments of the title molecules in neutral, positively, and negatively charged ions were studied using density functional method. Ground electronic state was assigned for each molecule. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that, besides ionic component, covalent bonds are formed between the metal s, d orbitals, and the p orbital of S, Se, and Te. For neutral and cationic molecules, the covalent character increases from ScX to CrX and from FeX to CuX with an exception of decrease at MnX and ZnX, while for anionic molecules, the trend is not obvious. For both neutral and charged molecules, the sulfides have the shortest bond distance and largest vibrational frequency, while tellurides have the largest bond distance and smallest vibrational frequency. For neutral and anionic molecules, the dissociation energy of sulfides is the largest, that of tellurides is the smallest, while this only remains true for cationic molecules from ScX+ to FeX+.