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首页> 外文期刊>RSC Advances >The reactions of α-amino acids and α-amino acid esters with high valent transition metal halides: synthesis of coordination complexes, activation processes and stabilization of α-ammonium acylchloride cations
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The reactions of α-amino acids and α-amino acid esters with high valent transition metal halides: synthesis of coordination complexes, activation processes and stabilization of α-ammonium acylchloride cations

机译：α-氨基酸和α-氨基酸酯与高价过渡金属卤化物的反应：配位化合物的合成，活化过程和α-酰氯铵阳离子的稳定化

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Titanium tetrachloride smoothly reacted with a selection of α-amino acids (aaH) in CH2Cl2 affording yellow to orange solid coordination compounds, 1a–d, in 70–78% yields. The salts [NHEt3][TiCl4(aa)], 2a–b, were obtained from TiCl4/aaH/NEt3 (aa = L-phenylalanine, N,N-dimethylphenylalanine), in 60–65% yields. The complex , 3, was isolated from the reaction of L-proline with NbCl5/NHiPr2, performed in CH2Cl2 at room temperature. The X-ray structure of 3 features a bridging (E)-1,2-bis(3,4-dihydro-2H-pyrrol-5-yl)ethene-1,2-diolate ligand, resulting from the unprecedented C–C coupling between two proline units. Unusually stable α-ammonium acyl chlorides were prepared by the reactions of PCl5/MCln (MCln = NbCl5, WCl6) with L-proline, N,N-dimethylphenylalanine, sarcosine and L-methionine. MX5 (M = Nb, Ta; X = F, Cl) reacted with L-leucine methylester and L-proline ethylester to give ionic coordination compounds, [MX4L2][MX6] (M = Nb, L = Me2CHCH2CH(NH2)CO2Me, X = F, 9; Cl, 11a; M = Nb, X = Cl, , 11c; Ta, 11d), in moderate to good yields. [NbCl5(Me2CHCH2CHNH3CO2Me)][NbCl6], 12, was isolated as a co-product of the reaction of NbCl5 with L-leucine isopropylester, and crystallographically characterized. The reaction of NbCl5 with L-serine isopropylester afforded NbCl3(OCH2CHNHCO2iPr), 13, in 66% yield. The activation of the ester O–R bond was observed in the reactions of L-leucine methyl ester with NbF5 and L-proline ethyl ester with MBr5 (M = Nb, Ta), these reactions proceeding with the release of EtF and EtBr, respectively. All the metal products were characterized by analytical and spectroscopic methods, while DFT calculations were carried out in order to provide insight into the structural and mechanistic aspects.
机译：四氯化钛在CH 2 Cl 2 中与选择的α-氨基酸（aaH）平稳反应生成黄色到橙色固体配位化合物1a-d，产率为70-78％。盐[NHEt 3 ] [TiCl 4 （aa）] 2a–b是从TiCl中获得的 4 / aaH / NEt 3 （aa = L -苯丙氨酸， N ， N -二甲基苯丙氨酸），收率为60–65％。从 L -脯氨酸与NbCl 5 / small> / NH i Pr 2 ，在CH 2 Cl 2 在室温下。 3的X射线结构特征为（ E ）-1,2-双（3,4-dihydro-2 H -吡咯-5-基）乙烯桥接-1,2-羟乙酸配体，是由于两个脯氨酸单元之间空前的C–C偶联而产生的。通过PCl 5 / MCl n sub> （MCl n = NbCl 5 ，WCl < sub> 6 ）和 L -脯氨酸， N ， N -二甲基苯丙氨酸，肌氨酸和 L -蛋氨酸。 MX 5 （M = Nb，Ta; X = F，Cl）与 L -亮氨酸甲酯和 L -脯氨酸乙酯生成离子配位化合物[MX 4 L 2 ] [MX < sub> 6 ]（M = Nb，L = Me 2 CHCH 2 CH（NH 2 ）CO 2 Me，X = F，9; Cl，11a; M = Nb，X ＝ Cl ，， 11c; Ta，11d），以中等至良好的产率。 [NbCl 5 （Me 2 CHCH 2 CHNH 3 CO 2 Me）] [NbCl 6 5 与 L -亮氨酸异丙酯反应的副产物，分离出12号[small>]，并进行晶体学表征。 NbCl 5 与 L -丝氨酸异丙酯的反应得到NbCl 3 （OCH 2 CHNHCO 2 i Pr），13 ，产率为66％。在 L -亮氨酸甲酯与NbF 5 和 L <的反应中观察到酯O–R键的活化。 / small>-脯氨酸乙酯与MBr 5 （M = Nb，Ta），这些反应分别进行，释放EtF和EtBr。所有金属产品都通过分析和光谱学方法进行了表征，同时进行了DFT计算，以便深入了解结构和机械方面。

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