2-(trimethylsilyl)ethyl 2-(benzyloxycarbonyl)amino-2-(dimethoxyphosphinyl)acetate | 134038-88-3

• 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: 2-(trimethylsilyl)ethyl 2-(benzyloxycarbonyl)amino-2-(dimethoxyphosphinyl)acetate
• 英文别名: 2'-trimethylsilylethyl 2-(benzyloxycarbonylamino)-2-(dimethoxyphosphoryl)acetate；Trimethylsilylethyl 2-(benzyloxycarbonylamino)-2-(dimethoxyphosphoryl)acetate；2-(trimethylsilyl)ethyl α-(dimethoxyphosphoryl)-N-(benzyloxycarbonyl)glycinate；N-Benzyloxycarbonyl-2-(dimethoxyphosphoryl)glycin-(2-trimethylsilylethyl)ester；Cbz-Phosgly-OTMSE；2-Trimethylsilylethyl 2-dimethoxyphosphoryl-2-(phenylmethoxycarbonylamino)acetate
• CAS: 134038-88-3
• 化学式: C₁₇H₂₈NO₇PSi
• 分子量: 417.471
• InChiKey: WXVZCKXMLXHXDD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.61
• 重原子数：
  27
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  100
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)ethyl 2-(benzyloxycarbonyl)amino-2-(dimethoxyphosphinyl)acetate 在 palladium 10% on activated carbon 氢气 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 20.0 ℃ 、100.0 kPa 条件下， 反应 0.5h， 生成 2-Trimethylsilylethyl 2-dimethoxyphosphoryl-2-[(2,2,2-trifluoroacetyl)amino]acetate
  参考文献：
  名称：

  WO2008/137779

  摘要：

  公开号：
• 作为产物：
  描述：

  {[(苄氧基)羰基]氨基}(羟基)乙酸 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 、 三氯化磷 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 32.0h， 生成 2-(trimethylsilyl)ethyl 2-(benzyloxycarbonyl)amino-2-(dimethoxyphosphinyl)acetate
  参考文献：
  名称：

  Synthesis of α- and β-Carbon-Linked Serine Analogues of the P^k Trisaccharide

  摘要：

  The synthesis of glycopeptide ligands for a range of biomedically relevant carbohydrate -binding proteins is a topic of great importance to the glycobiology community. This task is impeded by the inherent instability of glycosyl linkages to serine/threonine, the normal sites of O-glycosylation in proteins. We have previously developed methodology for the preparation of C-glycosylated serines based on catalytic asymmetric hydrogenation of the corresponding enamide esters with the DuPHOS-Rh+ catalysts. Here we report further development of the methodology in the preparation of the C-glycosyl serine analogue of the p(k) trisaccharide (alpha-Gal(1->4)beta-Gal(1->4)beta-Glc-CH2-serine); we require these ligands for our continuing investigations of the binding subunit of the shiga-like toxin. Catalytic asymmetric hydrogenation was used to prepare both alpha- and beta-C-glycosides in the R and S serine series. We report here on the tolerance of the DuPHOS catalysts toward acetate, benzoate, and benzyl hydroxyl protecting groups. Additionally, we have developed an amino acid protecting group strategy compatible with both asymmetric hydrogenation and solid-phase peptide synthesis. In the course of our studies, we have also developed a new methodology for regioselective reductive cleavage of benzylidene protecting groups.

  DOI：

  10.1021/jo991096m

文献信息

• Total Synthesis of the Biphenomycins; III¹.1 Synthesis of Biphenomycin B
  作者：Ulrich Schmidt、Regina Meyer、Volker Leitenberger、Helmut Griesser、Albrecht Lieberknecht

  DOI：10.1055/s-1992-26293

  日期：——

  The total synthesis of the cyclopeptide biphenomycin B (1b), a compound exhibiting a potent antibacterial activity against Gram-positive bacteria, is described. The non-proteinogenic amino acid (S,S)-diisotyrosine (2) was prepared by enantioselective hydrogenation of the corresponding didehydroamino acids. The 15-membered ansa ring was obtained in 85% yield within 5 minutes by ring closure of the appropriate linear pentafluorophenyl ester in the two phase system chloroform-aqueous sodium hydrogen carbonate without dilution.

  报道了环肽化合物双苯霉素B（1b）的全合成，该化合物展现出对革兰氏阳性细菌的强大抗菌活性。通过对应脱氢氨基酸的对映选择性氢化，合成了非蛋白质氨基酸（S，S）-二异酪氨酸（2）。在未经稀释的氯仿-水相碳酸氢钠两相体系中，通过适当线性五氟苯酯的环化反应，十五元ansa环在5分钟内以85%的产率获得。
• Diastereoselective Formation of (<i>Z</i>)-Didehydroamino Acid Esters
  作者：Ulrich Schmidt、Helmut Griesser、Volker Leitenberger、Albrecht Lieberknecht、Rainer Mangold、Regina Meyer、Bernd Riedl

  DOI：10.1055/s-1992-26143

  日期：——

  The rearrangement of (E)-didehydroamino acid derivatives to the corresponding Z-derivatives under acid or basic catalysis as well as under the influence of radicals has been investigated. The condensation of N-benzyloxycarbonyl or N-tert-butoxycarbonyl protected alkyl 2-amino-2-(dimethoxyphosphoryl)acetates with aldehydes or ketones in dichloromethane in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene furnishes (Z)-didehydroamino acid ester derivatives diastereoselectively in excellent yields and with high purity.

  研究了在酸或碱催化以及自由基影响下，(E)-二脱氢氨基酸衍生物重排为相应的 Z 衍生物的过程。在 1,8- 二氮杂双环[5.4.0]十一碳-7-烯存在下，N-苄氧羰基或 N-叔丁氧羰基保护的 2-氨基-2-(二甲氧基磷酰)乙酸烷基酯与醛或酮在二氯甲烷中缩合，可产生非对映选择性的 (Z)-二脱氢氨基酸酯衍生物，收率极高，纯度也很高。
• Total Synthesis of the Biphenomycins; V.¹Synthesis of Biphenomycin A
  作者：Ulrich Schmidt、Volker Leitenberger、Helmut Griesser、Johannes Schmidt、Regina Meyer

  DOI：10.1055/s-1992-26351

  日期：——

  The total synthesis of biphenomycin A is described. Two of the five stereogenic centres were formed by enantioselective hydrogenation of the corresponding didehydroamino acids using the rhodium-DIPAMP catalyst and the two stereogenic centres of the α-amino-β-hydroxy unit were created by enantioselective hydrogenation using the ruthenium-BINAP catalyst or via a stereoselective aldol condensation, respectively. The biphenyl structural element was constructed by a palladium(0)-catalyzed coupling reaction. The 15-membered ansa ring was closed in 85 % yield by use of the appropriate, linear pentafluorophenyl ester in the two phase system chloroform/aqueous sodium hydrogen carbonate.

  本文描述了联苯霉素 A 的全合成过程。五个立体中心中的两个是通过使用铑-DIPAMP 催化剂对相应的双脱氢氨基酸进行对映选择性氢化形成的，δ-氨基-δ-羟基单元的两个立体中心分别是通过使用钌-BINAP 催化剂进行对映选择性氢化或通过立体选择性醛醇缩合形成的。联苯结构单元是通过钯（0）催化的偶联反应生成的。在氯仿/水性碳酸氢钠两相体系中，使用适当的线性五氟苯基酯封闭 15 元的安萨环，收率为 85%。
• Efficient stereoselective preparation of protected isodityrosines
  作者：Kåre B. Jørgensen、Odd R. Gautun

  DOI：10.1016/s0040-4020(99)00576-1

  日期：1999.8

  A method for stereoselective preparation of isodityrosines with identical and orthogonal protecting groups is reported. The isodityrosines holding identical protecting groups were prepared from isovaniline in a three step procedure, in 50-64 % yield (> 98% ee, 84-96% de). Isodityrosine holding four orthogonal groups was prepared in four steps from isovaniline in 20 % total yield (> 98% ee, 87% de). (C) 1999 Elsevier Science Ltd. All rights reserved.
• Schmidt, Ulrich; Meyer, Regina; Leitenberger, Volker, Angewandte Chemie, 1989, vol. 101, # 7, p. 946 - 948
  作者：Schmidt, Ulrich、Meyer, Regina、Leitenberger, Volker、Lieberknecht, Albrecht

  DOI：——

  日期：——