Alpha hydroxylation of carboxylic acids with molecular oxygen catalyzed by the alpha oxidase of peas (Pisum sativum) - a novel biocatalytic synthesis of enantiomerically pure (R)-2-Hydroxy Acids
Alpha hydroxylation of carboxylic acids with molecular oxygen catalyzed by the alpha oxidase of peas (Pisum sativum) - a novel biocatalytic synthesis of enantiomerically pure (R)-2-Hydroxy Acids
复制标题
豌豆 (Pisum sativum) 的 α 氧化酶催化羧酸与分子氧的 α 羟基化 - 一种对映体纯 (R)-2-羟基酸的新型生物催化合成
DOI：
--
复制
发表时间：
1998
期刊：
影响因子：
--
通讯作者：
P. Schreier
中科院分区：
文献类型：
--
作者：
W. Adam*;W. Boland;J. Hartmann;H. Humpf;M. Lazarus;A. Saffert;C. R. Saha;P. Schreier
豌豆（Pisum sativum）的酶提取物对饱和、不饱和和含杂原子（氧、硫）羧酸1的α氧化的底物选择性表明，这种生物转化进行高度对映选择性。在豌豆α氧化酶催化下，长链羧酸与分子氧发生α-羟基化反应，首次在半制备规模（1 mmol）上合成了光学纯的2-羟基酸2。对于链中含有硫原子的衍生物，没有观察到磺基氧化。官能团（碳双键和三键、氧原子和硫原子）必须距离羧酸基团至少三个碳原子，以实现有效的不对称羟基化。通过与真实参比化合物的气相色谱数据的比较以及通过激子耦合圆二色性（ECCD）方法的应用，分配2-羟基酸2的绝对构型。这种前所未有的不对称性……
The substrate selectivities of the α oxidation of saturated, unsaturated, and heteroatom-containing (oxygen, sulfur) carboxylic acids 1 by the enzyme extract of peas (Pisum sativum) indicate that this biotransformation proceeds highly enantioselectively. For the first time, the synthesis of optically pure 2-hydroxy acids 2 has been achieved on the semipreparative scale (1 mmol) by α hydroxylation of long-chain carboxylic acids with molecular oxygen, catalyzed by the α oxidase of peas. For derivatives with sulfur atom in the chain, no sulfoxidation is observed. The functionalities (carbon double and triple bonds, oxygen, and sulfur atoms) must be at least three carbon atoms away from the carboxylic acid group to achieve efficient asymmetric hydroxylation. The absolute configuration of the 2-hydroxy acids 2 was assigned by comparison of the gas-chromatographic data with that of authentic reference compounds and by application of the exciton-coupled-circular-dichroism (ECCD) method. This unprecedented asymme...