Application of biocatalysts for development of non-natural organosilicon compounds

比较研究是由有机化合物的acyl受体[Me_3Si（CH_2）_nOH]和相关碳化合物[Me_3C（CH_2）_nOH]在立体声测定中的2-（4-氯苯氧基）丙酸盐的使用中产生的。The organosilicon compounds were effectively used as the substrates for the esterification of D-acid enantiomer。不同链的有机化合物-在硅原子和羟基组之间的长度之间，三甲基硅基甲基（n=1）使酯化反应既迅速又高度立体化，但具有传统基础的困难性，就像其碳的反面一样。在另一手上，在酶活性和立体声荧光中观察到三甲基酰亚胺（n=2）及其碳模拟（3，3-二甲基丁醇）之间没有差异。这些结果表明，硅原子在C中被用作脂质酶中的微型碳原子。 ... More 由于三甲基磺酰亚胺醇，但在增强三甲基磺酰亚胺的反应活性中是有效的。这种差异可以解释硅原子特性的基础，例如其低电性和大原子半径与碳原子比较。在不同来源测试的、等同于酒精脱氢酶（HLADH）回收的多种有机化合物、硅替代的酒精，即氧化物活性的基础和可商业上可用的酒精脱氢酶。特别是，催化率在三甲基烷基醇[Me_3Si（CH_2）_nOH]之间的差异较大，但在碳模拟之间没有差异。因此，HLADH的活动在有机化合物中极大地和明显地影响了三甲基磺酰亚胺组[三甲基磺酰亚胺（n=1），27%;三甲基磺酰亚胺（n=2），212%;三甲基磺酰丙烷（n=3），65%; ethanol，100%]。These differences might result from beta-effect of trimethylsilyl group （stabilization of a negative charge in the silicon and a positive charge on the carbon to the silicon） by considering the possible Mechanisms for hydrogen transfer at HLADH active site。作为一项与HLADH、三甲基酰亚胺醇的动力学调查结果，已找到与其他人显示出高亲和力。更进一步，从硅替代中提取的HLADH活性的增强即使是通过使用电子吸引组中相应的碳模拟方法来提供的（例如，3-甲氧基-3-甲基丁醇）。Less（低）

Comparative studies were made of the use as acyl acceptor of organosilicon compounds [Me_3Si(CH_2)_nOH] and the corresponding carbon compounds [Me_3C(CH_2)_nOH] in the stereoselective esterification of 2-(4-chlorophenoxy)propanoic acid by the use of lipase OF 360 of candida cylindracea in water-saturated benzene. The organosilicon compounds were effectively used as the substrates for the esterification of D-acid enantiomer. Of the organosilicon compounds of different chain-length between the silicon atom and the hydroxyl group, trimethylsilylmethanol (n=1) enabled the esterification reaction to be both fast and highly stereoselective, which was difficult with conventional substrates such as its carbon counterpart. On the other hand, no difference was observed between trimethylsilylethanol (n=2) and its carbon analogue (3,3-dimethylbutanol) in the enzymatic activity and the stereoselectivity. These results indicate that the silicon atom behaved as a mimic carbon atom for lipase in the c … More ase of trimethylsilylethanol but was effective in enhancing the reactivity of trimethylsilylmethanol. The difference could be explained on the basis of the properties of silicon atom, such as its low electronegativity and big atomic radius compared with the carbon atom.Among the commercially available alcohol dehydrogenases from different sources tested, equine lliver alcohol dehydrogenase (HLADH) recognized several organosilicon compounds, sila-substituted alcohols, as a substrate and exhibited the oxidative activity. Especially, large differences in catalytic rates were observed between trimethylsilyl alcohols [Me_3Si(CH_2)_nOH] but not between the carbon analogues. Thus, the activity of HLADH was extremely and peculiarly affected by trimethylsilyl group in the organosilicon compounds [trimethylsilylmethanol (n=1), 27% ; trimethylsilylethanol (n=2), 212% ; trimethylsilylpropanol (n=3), 65% ; ethanol, 100%]. These differences might result from beta-effect of trimethylsilyl group (stabilization of a negative charge in the carbon to the silicon and ・ a positive charge on the carbon to the silicon) by considering the possible mechanisms for hydrogen transfer at HLADH active site. As a result of kinetic investigations with HLADH, trimethylsilylethanol was found to show high affinity compared with the others. Furthermore, enhancement of HLADH activity derived from sila-substitution was not easily provided even by the use of the corresponding carbon analogues with electron attractive group (for example, 3-methoxy-3-methylbutanol). Less