(2R,4S)-2-Carboxymethyl-5,5-dimethyl-thiazolidine-4-carboxylic acid | 83375-88-6

• 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
• 英文名称: (2R,4S)-2-Carboxymethyl-5,5-dimethyl-thiazolidine-4-carboxylic acid
• 英文别名: (2R,4S)-2-(carboxymethyl)-5,5-dimethyl-1,3-thiazolidine-4-carboxylic acid
• CAS: 83375-88-6
• 化学式: C₈H₁₃NO₄S
• 分子量: 219.262
• InChiKey: MUFWBYXGWAWCFK-XINAWCOVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.36
• 重原子数：
  14.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  86.63
• 氢给体数：
  3.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  (2S-顺式)-3,3-二甲基-7-氧代-4-硫杂-1-氮杂双环[3.2.0]庚烷-2-羧酸 在 铜 作用下， 以 水 为溶剂， 生成 (2R,4S)-2-Carboxymethyl-5,5-dimethyl-thiazolidine-4-carboxylic acid
  参考文献：
  名称：

  金属离子催化水解某些β-内酰胺类抗生素

  摘要：

  金属（II）离子在30°水中的一些pencillin和头孢菌素衍生物的水解反应显示出饱和动力学。在金属离子和青霉素之间形成1：1的络合物，该络合物被氢氧根离子攻击的速度比未配位化合物快10 8倍。青霉素类和铜（统筹的部位II）离子是β内酰胺氮和羧酸基团。头孢菌素和金属离子的缔合常数大于青霉素的缔合常数，但头孢菌素与氢氧根离子反应的过渡态与金属离子的结合较不紧密。金属离子引起的速率提高的顺序为Cu II > Zn II > Ni II〜Co II。金属离子被认为稳定了由氢氧根离子攻击β-内酰胺形成的四面体中间体。关于金属离子作为酶中的亲电催化剂的一些评论。

  DOI：

  10.1039/p29800001725

文献信息

• Proctor, Philip; Gensmantel, Nigel P.; Page, Michael I., Journal of the Chemical Society. Perkin transactions II, 1982, p. 1185 - 1192
  作者：Proctor, Philip、Gensmantel, Nigel P.、Page, Michael I.

  DOI：——

  日期：——
• .beta.-Secondary and Solvent Deuterium Kinetic Isotope Effects and the Mechanisms of Base- and Acid-Catalyzed Hydrolysis of Penicillanic Acid
  作者：S. A. Deraniyagala、S. A. Adediran、R. F. Pratt

  DOI：10.1021/jo00111a020

  日期：1995.3

  beta-Secondary and solvent deuterium kinetic isotope effects have been determined at 25 degrees C for the alkaline and acid-catalyzed hydrolysis of penicillanic acid. In order to determine the former isotope effect, [6,6-H-2(2)]dideuteriopenicillanic acid has been synthesized. In alkaline solution, the former isotope effect (corrected to the effect of a single hydrogen orthogonal to the plane of the carbonyl group and for the inductive effect of deuterium) was found to be 0.95 +/- 0.01 and the latter 0.76 +/- 0.01. These values support the B(AC)2 mechanism of hydrolysis with rate-determining formation of the tetrahedral intermediate that has been proposed for other beta-lactams. The measured beta-secondary kinetic isotope for the acid-catalyzed reaction was 1.00 +/- 0.01. This represents a value averaged from experiments in 0.45 M HCl, 0.97 NI HCl, 4.5 M HCl, and 33.3 wt % H2SO4. All precedent suggests that this result would be very unlikely for an associative mechanism, such as that commonly observed (A(AC)2) for amide hydrolysis at these acid concentrations. Semiempirical AM1 calculations suggest that bicyclic beta-lactams are not only very weakly basic (in accord with previous experiment) but also protonate preferentially on nitrogen. This likelihood, taken with the secondary isotope effect, indicates that a likely pathway of acid-catalyzed hydrolysis would be that of an A(AC)1 mechanism with an intermediate acylium ion. If this were so, the calculated beta-secondary isotope effect per hydrogen coplanar with the breaking C-N bond and corrected for the inductive effect of deuterium would be 1.06 +/- 0.01. This suggests an early A(AC)1 transition state, which would be reasonable in this case because of destabilization of the N-protonated amide with respect to the acylium ion because of ring strain. The absence of specific participation by solvent in the transition state, as would be expected of an A(AC)1 but not an associative mechanism, is supported by the strongly inverse solvent deuterium kinetic isotope effect of 0.25 +/- 0.00 in 1 M HCl and 0.22 +/- 0.01 in 33.3 wt % H2SO4.