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Chiral Cobalt-Catalyzed Enantiomer-Differentiating Oxidation of Racemic Benzoins by Using Molecular Oxygen as Stoichiometric Oxidant

机译:分子氧作为化学计量氧化剂的手性钴催化对映体差异氧化外消旋苯甲酸酯

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摘要

Enantiopure secondary alcohols are useful key intermediates in asymmetric synthesis, pharmaceutical, agrochemical and fine chemical industries.[1] The kinetic resolution of racemic alcohol is an attractive method to obtain optically active alcohol[2, 3] especially in cases where other methods are not possible or provides poor enantioselectivity. Although excellent catalytic enantioselective methods are available for a variety of oxidations such as epoxidation,[4] dihydroxylation[5] and aziridination,[6] there are only very few methods available for enantioselective alcohol oxidation [Eq. (1)].[7] The pioneering work by Rychnovsky using chiral nitroxyl catalyst[8] followed by independent report of Stoltz[9] and Sigman[10] using chiral palladium complex made significant progress in oxidative kinetic resolution (OKR). Very recently, chiral vanadium catalyst developed by Toste[11] for the resolution of racemic a-hydroxy esters, chiral iridium catalyst developed by Ikariya,[12] chiral manganese catalyst[13] and chiral ruthenium catalysts[14] added strength to the field of asymmetric oxidation of secondary alcohols.
机译:对映纯仲醇是不对称合成,制药,农药和精细化工行业中有用的关键中间体。[1]外消旋醇的动力学拆分是获得旋光性醇[2,3]的一种有吸引力的方法,尤其是在其他方法不可行或对映选择性差的情况下。尽管出色的催化对映选择性方法可用于多种氧化反应,例如环氧化,[4]二羟基化[5]和叠氮化[6],但对映选择性醇氧化的方法很少。 (1)]。[7] Rychnovsky使用手性硝酰催化剂[8]的开创性工作,随后使用手性钯络合物的Stoltz [9]和Sigman [10]的独立报道在氧化动力学拆分(OKR)方面取得了重大进展。最近,Toste [11]开发的用于拆分外消旋α-羟基酯的手性钒催化剂,Ikariya开发的手性铱催化剂[12]手性锰催化剂[13]和手性钌催化剂[14]为该领域增添了力量仲醇的不对称氧化反应

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