ethyl (S)-3-amino-5-(trimethylsilyl)-4-pentynoate | 215738-15-1

• 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: ethyl (S)-3-amino-5-(trimethylsilyl)-4-pentynoate
• 英文别名: ethyl (S)-3-amino-5-trimethylsilyl-4-pentynoate；ethyl (3S)-3-amino-5-trimethylsilylpent-4-ynoate
• CAS: 215738-15-1
• 化学式: C₁₀H₁₉NO₂Si
• 分子量: 213.352
• InChiKey: OUWAIQPQYZYLGM-SECBINFHSA-N

物化性质

• 沸点：
  260.1±35.0 °C(Predicted)
• 密度：
  0.968±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.15
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  52.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl (S)-3-amino-5-(trimethylsilyl)-4-pentynoate 在 N-甲基吗啉 、 四丁基氟化铵 、 氯甲酸异丁酯 作用下， 生成 珍米洛非班
  参考文献：
  名称：

  A very short, efficient and inexpensive synthesis of the prodrug form of SC-54701A a platelet aggregation inhibitor

  摘要：

  A short and efficient synthesis of the prodrug form of SC-54701A has been achieved from (trimethylsilyl)acetylene in 6 steps with an overall yield of 19%. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0960-894x(97)00293-x
• 作为产物：
  描述：

  (αS)-[[3-(trimethylsilyl)-2-propynylidene]amino]benzeneethanol 在 sodium periodate 、 对甲苯磺酸 、 甲胺 、 锌 作用下， 以 四氢呋喃 、 乙醇 、 水 为溶剂， 反应 10.25h， 生成 ethyl (S)-3-amino-5-(trimethylsilyl)-4-pentynoate
  参考文献：
  名称：

  实用的对映合成β-取代的β-氨基酯

  摘要：

  开发了实用，大规模的β-氨基酯1的合成方法。将衍生自（S）-苯基甘醇和3-三甲基甲硅烷基丙醛的手性亚胺与具有高非对映选择性（de＞ 98％）的Reformatsky试剂3偶联，得到（SS）-4a作为主要异构体。在甲胺存在下，用高碘酸钠氧化裂解偶联产物4的氨基醇残基。观察到（SS）-异构体的不寻常的选择性氧化裂解，并且获得了ee＞ 99％的亚胺6，而没有裂解（RS）-4b异构体。与p-反应甲苯磺酸一水合物可以水解亚胺，并分离出胺盐。然后通过一锅法通过酯交换，甲硅烷基化和形成盐酸盐获得标题化合物1。该方法已成功应用于多种β-氨基酯的合成。

  DOI：

  10.1021/jo050177h

文献信息

• Use of enzyme penicillin acylase in selective amidation/amide hydrolysis to resolve ethyl 3-amino-4-pentynoate isomers
  作者：Ravindra S. Topgi、John S. Ng、Bryan Landis、Ping Wang、James R. Behling

  DOI：10.1016/s0968-0896(99)00155-8

  日期：1999.10

  and (S)-enantiomers of ethyl 3-amino-4-pentynoate in enantiomerically pure form employing the enzyme Penicillin acylase. In the acylation, phenylacetic acid was used as an acylating agent. We have shown that both the acylation and deacylation can be employed and that the activity of the enzyme Penicillin acylase can be controlled by maintaining an appropriate pH of the reaction medium.

  β-氨基酸，（S）-3-氨基-4-戊酸乙基酯，是一种手性合成子，用于合成抗血小板药盐酸西米洛非。开发了一种生物催化方法，以使用青霉素酰基转移酶分解对映体纯形式的3-氨基-4-戊酸乙酯的（R）-和（S）-对映体。在酰化中，使用苯基乙酸作为酰化剂。我们已经表明可以同时使用酰化和脱酰作用，并且可以通过维持反应介质的适当pH来控制青霉素酰基转移酶的活性。
• Kinetic Resolution of β-Amino Esters by Acylation Using Immobilized Penicillin Amidohydrolase
  作者：Bryan H. Landis、Patrick B. Mullins、Karen E. Mullins、Ping T. Wang

  DOI：10.1021/op0255130

  日期：2002.7.1

  Penicillin amidohydrolase [EC 3.5.1.11] was used to resolve stereoisomers of a beta-amino acid ester (ethyl 3-amino-5-(trimethylsilyl)-4-pentynoate) by phenylacetylation. After screening commercially available sources of the immobilized enzyme, one was found to be significantly more efficient, and this was developed at 1-L scale reaction. The effects of phenylacetic acid concentration, beta-amino acid ester concentration, and pH on bioconversion rates and side reactions were examined. The enzymatic reaction was monitored off-line by naphthoylation of samples and chiral analytical chromatography. The best conditions for the bioconversion were pH 5.7, 28 degreesC, and 14 000 units of enzyme activity per liter. The phenylacetic acid concentration was set at 50 g/L (0.37 M), and the amine at 100 g/L (0.47 M). Under these conditions, yields of the desired (S)amino acid ester were on the order of 90% with ee's of 95% or greater in less than 12 h. This process, along with a slight modification, was tested through 15 cycles at 0.4-L scale, and was scaled to 70 L. Recycle results extrapolated to approximately 25 reaction cycles before the enzyme lost 50% of its initial activity. Through three runs at 70 L, overall yield of (S)-amine was 42.7 +/- 0.6%, overall yield of (R)-phenylacetyl amide was 47.2 +/- 1.8%. The average ee of the amine (two runs) was 98.1 +/- 0.4%, for the amide the ee was 99.5 +/- 0.2%.
• Bioorg. Med. Chem. Lett. 1997, 7, 1699-1700
  作者：

  DOI：——

  日期：——
• A very short, efficient and inexpensive synthesis of the prodrug form of SC-54701A a platelet aggregation inhibitor
  作者：J. Cossy、A. Schmitt、C. Cinquin、D. Buisson、D. Belotti

  DOI：10.1016/s0960-894x(97)00293-x

  日期：1997.7

  A short and efficient synthesis of the prodrug form of SC-54701A has been achieved from (trimethylsilyl)acetylene in 6 steps with an overall yield of 19%. (C) 1997 Elsevier Science Ltd.
• Practical Enantioselective Synthesis of β-Substituted-β-amino Esters
  作者：Alok K. Awasthi、Mark L. Boys、Kimberly J. Cain-Janicki、Pierre-Jean Colson、Wendel W. Doubleday、Joseph E. Duran、Payman N. Farid

  DOI：10.1021/jo050177h

  日期：2005.7.1

  A practical, large-scale synthesis of a β-amino ester 1 was developed. A chiral imine derived from (S)-phenylglycinol and 3-trimethylsilylpropanal was coupled with the Reformatsky reagent 3 with high diastereoselectivity (de > 98%) to give (SS)-4a as the major isomer. The amino alcohol residue of the coupling product 4 was oxidatively cleaved with sodium periodate in the presence of methylamine. An

  开发了实用，大规模的β-氨基酯1的合成方法。将衍生自（S）-苯基甘醇和3-三甲基甲硅烷基丙醛的手性亚胺与具有高非对映选择性（de＞ 98％）的Reformatsky试剂3偶联，得到（SS）-4a作为主要异构体。在甲胺存在下，用高碘酸钠氧化裂解偶联产物4的氨基醇残基。观察到（SS）-异构体的不寻常的选择性氧化裂解，并且获得了ee＞ 99％的亚胺6，而没有裂解（RS）-4b异构体。与p-反应甲苯磺酸一水合物可以水解亚胺，并分离出胺盐。然后通过一锅法通过酯交换，甲硅烷基化和形成盐酸盐获得标题化合物1。该方法已成功应用于多种β-氨基酯的合成。