(alphaS)-1,3-二氢-alpha-[2-(甲硫基)乙基]-1,3-二氧代-2H-异吲哚-2-乙酸 | 29588-91-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: (alphaS)-1,3-二氢-alpha-[2-(甲硫基)乙基]-1,3-二氧代-2H-异吲哚-2-乙酸
• 英文名称: (2S)-4-methylthio-2-(1,3-dioxo-2-benzazole-2-yl)butanoic acid
• 英文别名: N-phthaloyl-L-methionine
• CAS: 29588-91-8
• 化学式: C₁₃H₁₃NO₄S
• mdl: MFCD00065027
• 分子量: 279.317
• InChiKey: VMTKJVHNTIEOCU-JTQLQIEISA-N

物化性质

• 熔点：
  124 °C(Solv: water (7732-18-5); methanol (67-56-1))
• 沸点：
  492.0±40.0 °C(Predicted)
• 密度：
  1.422±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  100
• 氢给体数：
  1
• 氢受体数：
  5

安全信息

• 海关编码：
  2930909090

反应信息

• 作为反应物：
  描述：

  (alphaS)-1,3-二氢-alpha-[2-(甲硫基)乙基]-1,3-二氧代-2H-异吲哚-2-乙酸 在 Beauveria caledonica ATCC 64970 、 一水合肼 作用下， 以 乙醇 为溶剂， 反应 74.0h， 生成 (S_CS_S)-L-methionine sulfoxide
  参考文献：
  名称：

  Biocatalytic and chemical routes to all the stereoisomers of methionine and ethionine sulfoxides

  摘要：

  Biotransformations of the N-phthaloyl derivatives of D- and L-methionine and of D- and L-ethionine by Beauveria bassiana ATCC 7159 or Beauveria caledonica ATCC 64970 produce the corresponding (S-S) sulfoxides in good yield and diastereomeric excess. Pure (SSSC) diastereomers can be obtained from L-series substrates by crystallisation of the biotransformation extract, and the corresponding (SSRC) products obtained from D-series substrates by chromatography of the biotransformation extract. Hydrogen peroxide-catalysed oxidation of the N-phthaloyl derivatives of D- and L-methionine and of D- and L-ethionine gives diastereomeric mixtures from which the (SSSC) and (RSRC) diastereomers can be obtained by crystallisation, and the (SSRC) and (RSSC) diastereomers obtained by chromatography. N-Cbz- and N-t-Boc methionines are also converted to sulfoxides with predominant (S-S) configuration by both B, bassiana and B. caledonica, but the isolated yields and d.e. of products were generally lower than those obtained from the N-phthaloyl substrates.Removal of the N-phthaloyl group from diastereomerically pure methionine and ethionine sulfoxides gave the corresponding amino acid sulfoxides in high yield; removal of N-Cbz and N-t-Boc groups from protected methionine sulfoxides was also achieved without loss of configuration at sulfur. (C) 1994 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00271-2
• 作为产物：
  描述：

  苯酐 、 L-蛋氨酸 在 溶剂黄146 作用下， 生成 (alphaS)-1,3-二氢-alpha-[2-(甲硫基)乙基]-1,3-二氧代-2H-异吲哚-2-乙酸
  参考文献：
  名称：

  Trifluoroborane-Catalyzed C–H Functionalization/S–H Insertion Reaction: Construction of N,S-Acetal Quaternary Centers

  摘要：

  三氟硼烷催化的α-重氮磷酸酯与硫醇的C-H官能化/S-H插入反应已经被开发出来。已经提出了一个合理的反应机理来理解这个复合反应。这个过程以中等到良好的产率和化学选择性提供了直接访问含有季铵中心的N,S-缩醛。

  DOI：

  10.1055/s-0034-1380384

文献信息

• Synthèse d'analogues structuraux de l'élédoïsine. 1^repartie: Préparation des produits intermédiaires
  作者：Ed. Sandrin、R. A. Boissonnas

  DOI：10.1002/hlca.19630460518

  日期：——

  The preparation of new dipeptides and tripeptides, which are useful intermediates in the synthesis of Eledoisin analogues, is described.

  描述了新的二肽和三肽的制备，它们是Eledoisin类似物合成中的有用中间体。
• Primary, Secondary, and Tertiary γ-C(sp³)–H Vinylation of Amides via Organic Photoredox-Catalyzed Hydrogen Atom Transfer
  作者：Hui Chen、Liangliang Guo、Shouyun Yu

  DOI：10.1021/acs.orglett.8b02737

  日期：2018.10.5

  An efficient strategy for primary, secondary and tertiary aliphatic γ-C(sp3)–H vinylation of amides with alkenylboronic acids is reported. These reactions are catalyzed by visible-light organic photoredox agents. Regioselective γ-C(sp3)–H vinylation of amides is controlled by a 1,5-hydrogen atom transfer of an amidyl radical generated in situ.

  据报道，用烯基硼酸对酰胺的伯，仲和叔脂族γ-C（sp 3）-H进行乙烯基化的有效策略。这些反应由可见光有机光氧化还原剂催化。酰胺的区域选择性γ-C（sp 3）–H乙烯基化是由就地生成的mid基的1，5-氢原子转移控制的。
• Chiral sensors for determining the absolute configurations of α-amino acid derivatives
  作者：Zhongxiang Chen、Hongjun Fan、Shiwei Yang、Guangling Bian、Ling Song

  DOI：10.1039/c8ob01933a

  日期：——

  A simple strategy for configurational assignments of alpha-amino acids has been developed by comparison of the proton NMR chemical shift values of the alpha hydrogens of N-phthaloyl protected alpha-amino acids in the presence of (R)-CSA 1 and (S)-CSA 1, respectively. Highly resolved NMR spectra can be obtained directly on the mixed solution of the chiral solvating agents with N-phthaloyl protected

  通过比较在（R）-CSA 1和（S）存在下N-邻苯二甲酰基保护的α-氨基酸的α氢的质子NMR化学位移值，开发了一种简单的α-氨基酸构型分配策略-CSA 1。可以在NMR管中直接在手性溶剂化剂与N-邻苯二甲酰基保护的α-氨基酸的混合溶液上获得高分辨的NMR光谱，从而给出可明显区分的质子信号而不会产生干扰，从而显着提高了分配的准确性并加快了分配过程。该策略广泛适用于各种天然和非天然氨基酸。
• Intramolecular carbenoid ylide forming reactions of 2-diazo-3-keto-4-phthalimidocarboxylic esters derived from methionine and cysteine
  作者：Marc Enßle、Stefan Buck、Roland Werz、Gerhard Maas

  DOI：10.3762/bjoc.8.49

  日期：——

  three steps. Upon rhodium-catalysed dediazoniation, two intramolecular carbenoid reactions competed, namely the formation of a cyclic sulfonium ylide and that of a six-ring carbonyl ylide. The S-methyl and S-benzyl ylides 12a and b could be isolated, while S-allyl ylide 12c underwent a [2,3]-sigmatropic rearrangement. The short-lived carbonyl ylides derived from methionine and S-benzylcysteine formed head-to-tail

  蛋氨酸、S-苄基半胱氨酸和S-烯丙基半胱氨酸分三步转化为2-重氮-3-氧代-4-邻苯二甲酰亚胺甲酸酯8a-c。在铑催化的脱重氮反应中，两个分子内类胡萝卜素反应竞争，即形成环状锍叶立德和六环羰基叶立德。可以分离S-甲基和S-苄基叶立德12a和b，而S-烯丙基叶立德12c经历[2,3]-σ重排。由甲硫氨酸和 S-苄基半胱氨酸衍生的短寿命羰基叶立德通过 [3 + 3]-环加成形成头尾二聚体，并且可以被外部亲偶极试剂捕获，而 S-烯丙基衍生物 14c 通过以下方式产生五环化合物 17分子内[3 + 2]-环加成反应。
• Probing the stereochemistry of the active site of gamma-glutamyl transpeptidase using sulfur derivatives of l-glutamic acid
  作者：Christian Lherbet、Jeffrey W. Keillor

  DOI：10.1039/b310767a

  日期：——

  Gamma-glutamyl transpeptidase (GGT) catalyses the transfer of a γ-glutamyl moiety from a donor substrate to different acceptors, such as amino acids and water. GGT is known to display relatively low stereospecificity with respect to the α-stereocentre of its donor substrates. In this study we have studied its stereospecificity with respect to the stereocentre at the δ-position of different analogues of L-glutamic acid. Notably, L-methionine sulfoxide is well-recognised whereas L-methionine sulfone and L-methionine sulfoximine are not. Furthermore, when the synthetic γ-diastereoisomers of L-methionine sulfoxide were separated and tested, it was discovered that GGT shows remarkable stereospecificity at the γ-position, binding the SCSS diastereoisomer with a Ki of 3.5 mM, whereas the SCRS diastereoisomer is not recognised. Finally, using a sulfoxide as a new pharmacophore for GGT, we have synthesized and tested an analogue of glutathione to obtain a very promising competitive inhibitor with a Ki of (53 ± 3) µM.

  γ-谷氨酰转肽酶 (GGT) 催化 γ-谷氨酰部分从供体底物转移到不同的受体，例如氨基酸和水。已知 GGT 相对于其供体底物的 α-立体中心表现出相对较低的立体特异性。在本研究中，我们研究了其相对于 L-谷氨酸不同类似物的 δ 位立体中心的立体特异性。值得注意的是，L-甲硫氨酸亚砜已被广泛认可，而 L-甲硫氨酸砜和 L-甲硫氨酸亚砜亚胺则不然。此外，当分离和测试合成的L-蛋氨酸亚砜的γ-非对映异构体时，发现GGT在γ-位表现出显着的立体特异性，以3.5 mM的Ki结合SCSS非对映异构体，而SCRS非对映异构体则未被识别。最后，使用亚砜作为GGT的新药效团，我们合成并测试了谷胱甘肽的类似物，获得了一种非常有前途的竞争性抑制剂，其Ki为（53±3） µM。