甲基N-[(烯丙氧基)羰基]-L-丝氨酸酯 | 136194-92-8

• 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: 甲基N-[(烯丙氧基)羰基]-L-丝氨酸酯
• 英文名称: (S)-N-Aloc-Ser-OMe
• 英文别名: Allyloxycarbonyl-L-serine methyl ester；methyl (2S)-3-hydroxy-2-(prop-2-enoxycarbonylamino)propanoate
• CAS: 136194-92-8
• 化学式: C₈H₁₃NO₅
• 分子量: 203.195
• InChiKey: XPTLNJORYQFACC-LURJTMIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  14
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  84.9
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  甲基N-[(烯丙氧基)羰基]-L-丝氨酸酯 在 四氮唑 、 叔丁基过氧化氢 、 phosphate buffer 、 L-半胱氨酸 、 lipase from Aspergillus niger 、 2-[4-[(3R,5R,8R,9S,10S,12S,13R,14S,17R)-3,12-二羟基-10,13-二甲基-2,3,4,5,6,7,8,9,11,12,14,15,16,17-十四氢-1H-环戊并[a]菲-17-基]戊酰氨基]乙烷磺酸 、 1-羟基苯并三唑 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 、 二异丙胺 、 N,N-二异丙基乙胺 、 papain 作用下， 以 二氯甲烷 、 丙酮 、 乙腈 为溶剂， 反应 35.67h， 生成 N-Allyloxycarbonyl-O-(3'-O-acetyl-6-N-phenylacetyl-2'-deoxycytidine-allyl-phosphato)-L-seryl-glycyl-L-aspartic acid γ-allyl ester
  参考文献：
  名称：

  Chemoenzymatic Synthesis of Nucleopeptides

  摘要：

  Nucleoproteins, in which the hydroxy group of a serine, a threonine, or a tyrosine, is linked through a phosphodiester group to the 3'- or 5'-end of DNA or RNA, play decisive roles in important biological processes. They may even have a major part in the process of viral replication by nucleoprotein-primed elongation of the oligonucleotide strand. For the study of the biological phenomena, in which nucleoproteins are involved, nucleopeptides with the characteristic linkage between the peptide chain and the oligonucleotide of their parent nucleoproteins may serve as powerful tools. However, the synthesis of these compounds is complicated by their pronounced acid- and base-lability, as well as their multifunctionality. As a result, protecting groups, which can be removed under the mildest conditions, are required. For the construction of such peptide conjugates using a flexible building block strategy, a combination of enzyme-labile and chemical protecting groups was developed. The C-terminal blocking function can be removed selectively from fully protected nucleoamino acid methyl, 2-methoxyethyl (ME), and methoxyethoxyethyl (MEE) esters by saponification of the esters. After elongation of the peptide chain with amino acid or peptide methyl, ME, MEE, and choline esters, the C-terminal ester blocking group can again be removed easily. The methyl, ME, and MEE esters are cleaved off with lipase, and the choline ester group is selectively attacked by butyrylcholine esterase. The nucleoamino acids and peptides formed may be fully deprotected. To this end, the enzyme-labile N-phenylacetyl (PhAc) group, which was employed to mask the amino functions of the nucleobases, was removed. The O-acetate in the deoxyribose was saponified, and the allyl protecting groups present were cleaved by Pd-0-mediated allyl transfer. By combination of these techniques, a nucleopeptide was produced, which represents the characteristic linkage region of the nucleoprotein of adenovions 2. The conditions, under which the enzymatic deprotections proceed, are so mild that no undesired side reaction is observed, that is no depurination or beta elimination of the nucleosides occurs. In addition, the specificity of the biocatalysts ensures that the peptide bonds and the other protecting groups present are not attacked either.

  DOI：

  10.1002/(sici)1521-3765(19990201)5:2<669::aid-chem669>3.0.co;2-v
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 甲基N-[(烯丙氧基)羰基]-L-丝氨酸酯
  参考文献：
  名称：

  Polymer-bound p-alkoxybenzyl trichloracetimidates: Reagents for the protection of alcohols as benzyl ethers on solid-phase

  摘要：

  Wang and Tentagel resins were convened into their trichloroacetimidate dervatives and used as polymer-bound benzylating reagents for a variety of alcohols. Loading and cleavage proceed in good to excellent yields in the presence of BF3.OEt2 and 1% TFA respectively. The resins have excellent shelf life. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(97)10684-0

文献信息

• A Mild Ligand-Free Iron-Catalyzed Liberation of Alcohols from Allylcarbonates
  作者：André P. Dieskau、Bernd Plietker

  DOI：10.1021/ol202270g

  日期：2011.10.21

  from most carbonates the allyloxy carbonyl protecting group can be cleaved under neutral conditions using metal catalysis. However, most of the catalysts employed to date are based upon precious metals. Herein we present two protocols for the mild Fe-catalyzed liberation of alcohols from allylcarbonates that are characterized by broad functional group tolerance and exclusive chemoselectivity.

  与大多数碳酸盐不同，烯丙氧基羰基保护基可以在中性条件下使用金属催化裂解。然而，迄今为止使用的大多数催化剂是基于贵金属的。本文中，我们提出了两种温和的铁催化从烯丙基碳酸酯中释放醇的方案，其特征在于宽泛的官能团耐受性和独有的化学选择性。
• 一种1-氮杂-5-锗杂-5-烷基二环[3.3.3]十一 烷类化合物、合成方法及应用
  申请人：中国科学技术大学

  公开号：CN108047268B

  公开（公告）日：2020-05-01

  本发明提供了一种具有式I所示结构的1‑氮杂‑5‑锗杂‑5‑烷基二环[3.3.3]十一烷类化合物，拓展了1‑氮杂‑5‑锗杂‑5‑烷基二环[3.3.3]十一烷化合物的种类，并且本发明提供的化合物可作为亲核试剂，该亲核试剂对空气、湿度条件均稳定，并且与芳基卤素进行Ge‑Stille偶联反应的反应效率高。
• Remarkably efficient activation of glycosyl trichloro- and (N-phenyl)trifluoroacetimidates with bismuth(III) triflate
  作者：Matteo Adinolfi、Alfonso Iadonisi、Alessandra Ravidà、Silvia Valerio

  DOI：10.1016/j.tetlet.2006.02.034

  日期：2006.4

  Easily handled and nontoxic Bi(OTf)(3) is a powerful activator for trichloro- and (N-phenyl)trifluoroacetimidate glycosyl donors. This catalyst allows glycosidations to be performed at low temperatures in very short times. Rewarding yields were obtained from a wide range of donors of varying reactivity. (c) 2006 Elsevier Ltd. All rights reserved.
• Synthesis of <i>O</i>-β-Galactopyranosyl-L-Serine Derivatives Using β-Galactosidase in Aqueous-Organic Reaction Systems
  作者：K.-C. Becker、P. Kuhl

  DOI：10.1080/07328309908543986

  日期：1999.1.1

  The galactosylation of amino protected serine methyl ester derivatives by beta-galactosidases from E. coli and A. oryzae in aqueous-organic solvents was investigated. A comparison of enzyme activity in aqueous buffer and in several aqueous-organic mixtures revealed that the presence of an organic solvent normally causes a loss in enzyme activity. When the enzyme is used in suspensions with mainly undissolved lactose, the detrimental influence of an organic solvent is less marked if it does not exceed 25 % of the added mixture with water. Employing organic cosolvents, such as acetonitrile, 2-butanone, acetone or ethyl acetate, we obtained yields of the desired galactosylation products higher than those with the enzyme in purely aqueous solution. The amino protecting group shows a significant influence on the transglycosylation reaction in terms of yield, the best up to 28 % being achieved in the synthesis of Aloc-(Gal beta 1-)Ser-OMe with beta-galactosidase from E. coli in a reaction mixture containing 8 to 15 % organic solvent.
• Chemoenzymatic Synthesis of Nucleopeptides
  作者：Stefanie Flohr、Volker Jungmann、Herbert Waldmann

  DOI：10.1002/(sici)1521-3765(19990201)5:2<669::aid-chem669>3.0.co;2-v

  日期：1999.2.1

  Nucleoproteins, in which the hydroxy group of a serine, a threonine, or a tyrosine, is linked through a phosphodiester group to the 3'- or 5'-end of DNA or RNA, play decisive roles in important biological processes. They may even have a major part in the process of viral replication by nucleoprotein-primed elongation of the oligonucleotide strand. For the study of the biological phenomena, in which nucleoproteins are involved, nucleopeptides with the characteristic linkage between the peptide chain and the oligonucleotide of their parent nucleoproteins may serve as powerful tools. However, the synthesis of these compounds is complicated by their pronounced acid- and base-lability, as well as their multifunctionality. As a result, protecting groups, which can be removed under the mildest conditions, are required. For the construction of such peptide conjugates using a flexible building block strategy, a combination of enzyme-labile and chemical protecting groups was developed. The C-terminal blocking function can be removed selectively from fully protected nucleoamino acid methyl, 2-methoxyethyl (ME), and methoxyethoxyethyl (MEE) esters by saponification of the esters. After elongation of the peptide chain with amino acid or peptide methyl, ME, MEE, and choline esters, the C-terminal ester blocking group can again be removed easily. The methyl, ME, and MEE esters are cleaved off with lipase, and the choline ester group is selectively attacked by butyrylcholine esterase. The nucleoamino acids and peptides formed may be fully deprotected. To this end, the enzyme-labile N-phenylacetyl (PhAc) group, which was employed to mask the amino functions of the nucleobases, was removed. The O-acetate in the deoxyribose was saponified, and the allyl protecting groups present were cleaved by Pd-0-mediated allyl transfer. By combination of these techniques, a nucleopeptide was produced, which represents the characteristic linkage region of the nucleoprotein of adenovions 2. The conditions, under which the enzymatic deprotections proceed, are so mild that no undesired side reaction is observed, that is no depurination or beta elimination of the nucleosides occurs. In addition, the specificity of the biocatalysts ensures that the peptide bonds and the other protecting groups present are not attacked either.