Dipartimento di Chimica and CNR ICCOM, Università di Bari via Orabon 4, 70125 Bari, Italy.
Chemistry. 2009 Dec 14;15(48):13417-26. doi: 10.1002/chem.200902110.
An experimental investigation of the enantioselective oxidation of aryl benzyl sulfides by tert-butyl hydroperoxide in the presence of a titanium/hydrobenzoin catalyst has shown that these sulfides are ideal substrates for this catalytic system, with negligible interference by the substituents on the aryl groups. A reaction mechanism based on DFT computations has been proposed. The DFT MPWB1K functional was used in the theoretical investigation to account for weak hydrogen-bonding and pi interactions. The computed reaction profile explains the experimentally observed enantioselectivity, which is determined by the thermodynamics of the first phase of the reaction. A detailed discussion of the hydrogen-bonding and pi interactions that drive the reaction along the observed stereochemical path is given.
在手性钛/二氢苯并呋喃催化剂存在下，过氧化叔丁醇对芳基苄基硫醚的对映选择性氧化的实验研究表明，这些硫醚是该催化体系的理想底物，芳基上取代基的干扰可以忽略不计。提出了基于密度泛函理论计算的反应机理。在理论研究中使用了 DFT MPWB1K 函数来考虑弱氢键和 pi 相互作用。计算出的反应轮廓解释了实验观察到的对映选择性，这是由反应第一阶段的热力学决定的。详细讨论了驱动反应沿着观察到的立体化学途径的氢键和 pi 相互作用。
