methyl trans-3-(4-chlorophenyl)glycidate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl trans-3-(4-chlorophenyl)glycidate
• 英文别名: methyl trans-4-chloro phenylglycidate；methyl (2S,3R)-3-(4-chlorophenyl)oxirane-2-carboxylate
• 化学式: C₁₀H₉ClO₃
• 分子量: 212.633
• InChiKey: VSNXKSFFZDSGMY-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl trans-3-(4-chlorophenyl)glycidate 在 sodium hydroxide 作用下， 生成 trans-3-(4-chlorophenyl)oxirane-2-carboxylic acid
  参考文献：
  名称：

  Design, Synthesis, and Evaluation of Aza-Peptide Epoxides as Selective and Potent Inhibitors of Caspases-1, -3, -6, and -8

  摘要：

  Aza-peptide epoxides, a novel class of irreversible protease inhibitors, are specific for the clan CD cysteine proteases. Aza-peptide epoxides with an aza-Asp residue at PI are excellent irreversible inhibitors of caspases-1, -3, -6, and -8 with second-order inhibition rates up to 1910 000 M-1 s(-1). In general, the order of reactivity of aza-peptide epoxides is S'S > R,R > trans > cis. Interestingly, some of the R,R epoxides while being less potent are actually more selective than the S,S epoxides. Our aza-peptide epoxides designed For caspases are stable, potent, and specific inhibitors, as they show little to no inhibition of other proteases such as the aspartyl proteases porcine pepsin, human cathepsin D, plasmepsin 2 from P. falciparum, HIV-1 protease, and the secreted aspartic proteinase 2 (SAP-2) from Candida albicans; the serine proteases granzyme B and alpha-chymotrypsin; and the cysteine proteases cathepsin B and papain (clan CA), and legumain (clan CD).

  DOI：

  10.1021/jm0305016
• 作为产物：
  描述：

  对氯肉桂酸 在 叔丁基过氧化氢 、 La-(S)-BINOL-Ph₃AsO 、 4 A molecular sieve 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 17.0h， 生成 methyl trans-3-(4-chlorophenyl)glycidate
  参考文献：
  名称：

  镧系元素-BINOL配合物催化α，β-不饱和羧酸咪唑化物和酰胺的不对称环氧化

  摘要：

  研究了α，β-不饱和羧酸咪唑化物和简单酰胺的高度对映选择性催化不对称环氧化反应。在5-10 mol％的镧系元素-BINOL配合物的存在下，反应在高底物普遍性下可顺利进行。特别地，在α，β-不饱和酰胺的情况下，几乎具有完美的对映选择性（> 99％ee）。相应的环氧化物已成功转化为多种类型的有用手性化合物，例如α，β-环氧酯，α，β-环氧酰胺，α，β-环氧醛，α，β-环氧β-酮酸酯，α-和β-羟基羰基化合物。进行B3LYP密度泛函研究以预测底物反应性。

  DOI：

  10.1016/j.tet.2003.06.010

文献信息

• Asymmetric synthesis and biological activities of natural product (+)-balasubramide and its derivatives
  作者：Jun Li、Jianzu Li、Yuan Xu、Yunjie Wang、Luyong Zhang、Li Ding、Yining Xuan、Tao Pang、Hansen Lin

  DOI：10.1080/14786419.2015.1071363

  日期：2016.4.2

  The natural product (+)-balasubramide (3j) and its derivatives (3a–3i) were synthesized using a two-step asymmetric synthesis, and the biological activities of 3a–3j were determined in vitro. Methyl (2S,3R)-(+)-3-phenyloxirane-2-carboxylate (1h), the asymmetric synthesis of which was described in a previous paper, was selected as the starting material. Compounds 3a–3j were evaluated for their neuroprotective

  通过两步不对称合成合成了天然产物（+）-巴拉舒酰胺（3j）及其衍生物（3a-3i），并在体外测定了3a-3j的生物活性。选择（2S，3R）-（+）-3-苯基环氧乙烷-2-羧酸甲酯（1h），它的不对称合成在先前的文章中进行了描述，被选为起始原料。化合物3a–3j对它们的神经保护，抗氧化和抗神经炎症作用进行了评估。（+）-Balasubramide及其在6-苯环中具有不同负电性基团的衍生物几乎不产生神经保护和抗氧化作用，但在BV-2小胶质细胞中诱导了强效的抗神经炎作用（3g例外）。化合物3c在其6-苯环中具有三氟甲基的化合物，是一种特别有效的抗神经炎药。这些结果证明（+）-巴拉舒布酰胺的6-苯基环的电负性是其对神经炎症抑制作用的重要决定因素。更多的负电性取代基可产生更强的抗神经炎作用。而且，细胞毒性测定表明所测试的化合物没有明显的作用。
• Highly efficient asymmetric synthesis of α,β-epoxy esters via one-pot organocatalytic epoxidation and oxidative esterification
  作者：Yi-ning Xuan、Han-Sen Lin、Ming Yan

  DOI：10.1039/c3ob00056g

  日期：——

  Highly enantioselective synthesis of α,β-epoxy esters was achieved via one-pot organocatalytic epoxidation and consequent oxidative esterification. Excellent enantioselectivities (up to 99% ee) and good yields were obtained for a variety of α,β-epoxy esters. The method was readily scaled. Furthermore the product was applied towards the synthesis of (−)-clausenamide with excellent enantioselectivities

  通过一锅式有机催化环氧化和随后的氧化酯化反应，可以实现α，β-环氧酯的高度对映选择性合成。对于各种α，β-环氧酯，均具有出色的对映选择性（高达99％ee）和良好的收率。该方法易于扩展。此外，将产物用于具有优异对映选择性（> 99％ee）的（-）-clausenamide的合成。
• A convenient synthesis of aziridine-2-carboxylic esters
  作者：Johan Legters、Lambertus Thijs、Binne Zwanenburg

  DOI：10.1002/recl.19921110101

  日期：——

  Optically active oxirane-2-carboxylic esters, prepared from allylic alcohols employing the Sharpless epoxidation, were treated with sodium azide. The azido alcohols obtained were subsequently converted into aziridine-2-carboxylic esters by reaction with triphenylphosphine, in good yields and with high optical purity. Various racemic oxirane-2-carboxylic esters were subjected to the same sequence of

  用叠氮化钠处理由使用Sharpless环氧化的烯丙基醇制备的旋光环氧乙烷-2-羧酸酯。随后通过与三苯基膦反应以高收率和高光学纯度将获得的叠氮基醇转化为氮丙啶-2-羧酸酯。使各种外消旋环氧乙烷-2-羧酸酯进行相同的反应顺序。
• Catalytic asymmetric epoxidation of α,β-unsaturated carboxylic acid imidazolides and amides by lanthanide–BINOL complexes
  作者：Takashi Ohshima、Tetsuhiro Nemoto、Shin-ya Tosaki、Hiroyuki Kakei、Vijay Gnanadesikan、Masakatsu Shibasaki

  DOI：10.1016/j.tet.2003.06.010

  日期：2003.12

  Highly enantioselective catalytic asymmetric epoxidation of α,β-unsaturated carboxylic acid imidazolides and simple amides was developed. In the presence of 5–10 mol% of lanthanide–BINOL complexes, the reaction proceeded smoothly with high substrate generality. In particular, in the cases of α,β-unsaturated amides, there was nearly perfect enantioselectivity (>99% ee). The corresponding epoxides were

  研究了α，β-不饱和羧酸咪唑化物和简单酰胺的高度对映选择性催化不对称环氧化反应。在5-10 mol％的镧系元素-BINOL配合物的存在下，反应在高底物普遍性下可顺利进行。特别地，在α，β-不饱和酰胺的情况下，几乎具有完美的对映选择性（> 99％ee）。相应的环氧化物已成功转化为多种类型的有用手性化合物，例如α，β-环氧酯，α，β-环氧酰胺，α，β-环氧醛，α，β-环氧β-酮酸酯，α-和β-羟基羰基化合物。进行B3LYP密度泛函研究以预测底物反应性。
• Regioselective syntheses of 3-hydroxy-4-aryl-3,4,5-trihydro-2H-benzo[b][1,4]diazepin-2(1H)-ones and 3-benzylquinoxalin-2(1H)-ones from arylglycidates when exposed to 1,2-diaminobenzenes
  作者：Vakhid A. Mamedov、Vera L. Mamedova、Victor V. Syakaev、Julia K. Voronina、Essam M. Mahrous、Dmitry E. Korshin、Shamil K. Latypov、Oleg G. Sinyashin

  DOI：10.1016/j.tet.2020.131478

  日期：2020.10

  ,4]diazepin-2(1H)-ones and 3-benzylquinoxalin-2(1H)-ones – obtained in reactions of 1,2-diaminobenzenes with methyl 3-arylglycidates in boiling acetic acid. Substituents in arylglycidates determine the direction of processes. Electron withdrawing substituents (NO2), halogen atoms (Cl, Br, F), as well as the absence of substituents, provide the formation of benzo[b][1,4]diazepin-2(1H)-one derivatives

  两类具有重要药理意义的化合物的代表– 3-羟基-4-芳基-3,4,5-三氢-2 H-苯并[ b ] [1,4]二氮杂-2-2 （1 H）-酮和3-苄基喹喔啉-2（1 H）-ones-由1,2-二氨基苯与3-芳基缩水甘油酸甲酯在沸腾的乙酸中反应制得。芳基缩水甘油酸酯中的取代基决定了过程的方向。吸电子取代基（NO2），卤素原子（Cl，Br，F）以及不存在取代基的情况下，形成了苯并[b] [1,4]二氮杂-2-2（1H）-一衍生物和电子捐赠基团（OMe，Me）有助于3-苄基喹喔啉-2（1H）-one的形成。结果，出现了3-羟基-4-芳基-3,4,5-三氢-2 H-苯并[[获得了b ] [1,4] diazepin-2（1 H）-one，并提出了一种新的制备3-苄基喹喔啉-2（1H）-one的方法。