methyl (2Z,4S)-4-(tert-butoxycarbonylamino)-2-methyl-2-pentenoate | 153829-61-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl (2Z,4S)-4-(tert-butoxycarbonylamino)-2-methyl-2-pentenoate
• 英文别名: methyl (Z,4S)-2-methyl-4-[(2-methylpropan-2-yl)oxycarbonylamino]pent-2-enoate
• CAS: 153829-61-9
• 化学式: C₁₂H₂₁NO₄
• 分子量: 243.303
• InChiKey: IDIXFDQUNONYNQ-FUOZMLNRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (2Z,4S)-4-(tert-butoxycarbonylamino)-2-methyl-2-pentenoate 在 4-二甲氨基吡啶 、 二碳酸二叔丁酯 作用下， 以 乙腈 为溶剂， 以85%的产率得到(S)-3,5-Dimethyl-2-oxo-2,5-dihydro-pyrrole-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Calyculins。C 26 -C 32片段的不对称合成

  摘要：

  从丙氨酸开始，已经设计出一种有效的和高度立体控制的方法，用于在花萼素C恶唑片段中的C 30和C 32处构建天然的顺式立体化学。可以从N-BOC-alaninal通过七个步骤访问标题片段本身。

  DOI：

  10.1016/0040-4039(94)85330-4
• 作为产物：
  描述：

  Boc-L-丙氨醛 、 以90%的产率得到methyl (2Z,4S)-4-(tert-butoxycarbonylamino)-2-methyl-2-pentenoate
  参考文献：
  名称：

  Calyculins。C 26 -C 32片段的不对称合成

  摘要：

  从丙氨酸开始，已经设计出一种有效的和高度立体控制的方法，用于在花萼素C恶唑片段中的C 30和C 32处构建天然的顺式立体化学。可以从N-BOC-alaninal通过七个步骤访问标题片段本身。

  DOI：

  10.1016/0040-4039(94)85330-4

文献信息

• Asymmetric Syntheses of α-Methyl γ-Amino Acid Derivatives
  作者：Ye Zhu、Sakunchai Khumsubdee、Amber Schaefer、Kevin Burgess

  DOI：10.1021/jo201215c

  日期：2011.9.16

  this reaction; syn-products were formed from the E-alkenes, while the Z-isomers gave anti-target materials, both with high diastereoselectivities. This study featured asymmetric catalysis to elaborate optically active substrates into more stereochemically complex chirons; we suggest that the approach used, optimization of stereocontrol by varying peripheral aspects of the substrate, tends to be easier

  进行该项目的目的是证明Crabtree催化剂“ cat ”的手性卡宾-恶唑啉类似物介导的不对称氢化在氨基酸的烯丙基胺衍生物的不对称氢化中的潜力。改变底物的外围特征（保护基，与氧化还原过程有关的官能团和烯烃的几何形状）以优化由底物施加的立体化学载体，并使它们与催化剂载体对齐。N-乙酰基保护，O -TBDPS-保护的烯丙基底物9a - e出现了最佳的反应效果。顺式产物是由E-烯烃形成的，而Z是-异构体提供了具有高非对映选择性的抗目标物质。这项研究的特点是不对称催化，将光学活性底物精制成更立体化学的螯合物。我们建议，对于每种类型的底物，所采用的方法通过改变底物的外围方面来优化立体控制，往往比从头设计催化剂更容易。换句话说，底物载体的优化可能比通过配体修饰来增强催化剂载体更容易。
• Purines. XXXIII. Syntheses and cytokinin activities of both enantiomers of 1'-methylzeatin and their 9-.BETA.-D-ribofuranosides.
  作者：Tozo FUJII、Taisuke ITAYA、Satoshi MATSUBARA

  DOI：10.1248/cpb.37.1758

  日期：——

  The structures and absolute configurations of the cytokinins 1'-methylzeatin and its 9-riboside, both secreted by Pseudomonas syringae pv savastanoi, have been established as [R-(E)]-2-methyl-4-(9H-purin-6-ylamino)-2-penten-1-ol[(1'R)-2] and [R-(E)]-N-(4-hydroxy-1, 3-dimethyl-2-butenyl)adenosine [(1''R)-4], respectively, as a result of the chiral syntheses of (1'R)- and (1'S)-1'-methylzeatins [(1'R)-2 and (1'S)-2] and of their 9-β-D-ribofuranosides [(1''R)-4 and (1''S)-4] from D- and L-alanines. These zeatin derivatives were tested for cytokinin activity in the tobacco callus and the lettuce seed germination bioassays. The "natural" enantiomer (1'R)-2 was found to be as active as zeatin (1) itself and more active than its 9-riboside [(1''R)-4]. The "unnatural" enantiomer (1'S)-2 and its 9-riboside [(1''S)-4] were less active than the corresponding natural cytokinins, (1'R)-2 and (1''R)-4, respectively.

  由 Pseudomonas syringae pv savastanoi 分泌的细胞分裂素 1'-methylzeatin 及其 9-riboside 的结构和绝对构型已被确定，分别为 [R-(E)]-2-甲基-4-(9H-嘌呤-6-基氨基)-2-戊烯-1-醇[(1'R)-2]和 [R-(E)]-N-(4-羟基-1、(1'R)-和(1'S)-1'-甲基玉米素[(1'R)-2 和 (1'S)-2]及其 9-β-D-ribofuranosides [(1'R)-4和 (1'S)-4]的手性合成。这些玉米素衍生物在烟草胼胝体和莴苣种子萌发生物测定中进行了细胞分裂素活性测试。结果发现，"天然 "对映体（1'R）-2 的活性与玉米素（1）本身相同，而且比其 9-核苷[（1''R）-4]的活性更高。非天然 "对映体（1'S）-2 及其 9-核苷[(1''S)-4]的活性分别低于相应的天然细胞分裂素（1'R）-2 和 (1''R)-4）。
• Synthesis of the C₂₆−C₃₂ Oxazole Fragment of Calyculin C:  A Test Case for Oxazole Syntheses
  作者：Petri M. Pihko、Ari M. P. Koskinen

  DOI：10.1021/jo971167m

  日期：1998.1.1

  The synthesis of the C-26-C-32 oxazole fragment 4 and its C-32 epimer 20 of serine/threonine protein phosphatase PP1 and PP2A inhibitor calyculin C is presented. The syn methyl arrangement in 4 was established through cyclic stereocontrol. Several methods for oxidizing the intermediate oxazolines 18 and 19 to the finished oxazole fragments were explored. The best results were obtained with oxidations proceeding through the corresponding ester enolate when the carbamate NH side chain was temporarily protected with a TMS group, or with CuBr2/DBU/HMTA-based oxidations. The finished oxazole fragment 4 was obtained in 21% overall yield, starting from Boc-D-alaninal.
• Calyculins. Asymmetric synthesis of the C26-C32 fragment
  作者：Ari M.P. Koskinen、Petri M. Pihko

  DOI：10.1016/0040-4039(94)85330-4

  日期：1994.10

  An efficient and highly stereocontrolled method for the construction of the natural syn stereochemistry at C30 and C32 in the calyculin C oxazole fragment has been devised starting from alanine. The title fragment itself is accessible in seven steps from N-BOC-alaninal.

  从丙氨酸开始，已经设计出一种有效的和高度立体控制的方法，用于在花萼素C恶唑片段中的C 30和C 32处构建天然的顺式立体化学。可以从N-BOC-alaninal通过七个步骤访问标题片段本身。