(R-(Z))-4-{[(1,1-dimethylethoxy)carbonyl]amino}-2-methyl-2-pentenoic acid methyl ester | 121358-04-1

• 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: (R-(Z))-4-{[(1,1-dimethylethoxy)carbonyl]amino}-2-methyl-2-pentenoic acid methyl ester
• 英文别名: methyl (Z,4R)-2-methyl-4-[(2-methylpropan-2-yl)oxycarbonylamino]pent-2-enoate
• CAS: 121358-04-1
• 化学式: C₁₂H₂₁NO₄
• 分子量: 243.303
• InChiKey: IDIXFDQUNONYNQ-UFGYOYAJSA-N

物化性质

• 熔点：
  49-50 °C
• 沸点：
  338.5±35.0 °C(predicted)
• 密度：
  1.029±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

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：

  (R-(Z))-4-{[(1,1-dimethylethoxy)carbonyl]amino}-2-methyl-2-pentenoic acid methyl ester 在 盐酸 、 Amberlite IRA-402 (HCO₃^1-) 、 二异丁基氢化铝 、 三乙胺 作用下， 以 乙醇 、 正己烷 、 二氯甲烷 、 水 、 正丁醇 为溶剂， 反应 5.25h， 生成 (1'R)-1'-methyl-cis-zeatin
  参考文献：
  名称：

  Syntheses of (1'R)-1'-Methyl-cis-zeatin and Its 9-b-D-Ribofuranoside

  摘要：

  DOI：

  10.3987/com-88-4636
• 作为产物：
  描述：

  Boc-D-丙氨酸甲酯 在 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 1.92h， 生成 (R-(Z))-4-{[(1,1-dimethylethoxy)carbonyl]amino}-2-methyl-2-pentenoic acid methyl ester
  参考文献：
  名称：

  Purines. XLV. Syntheses and cytokinin activities of the cis isomers of (1'R)-1'-methylzeatin and its 9-.BETA.-D-ribofuranoside.

  摘要：

  (1'R)-1'-甲基-顺式玉米素 (2b) 及其 9-β-D-呋喃核苷 (4b) 首次由 D-丙氨酸 (5) 经 7 个步骤合成。新的顺式玉米素衍生物 2b 和 4b 以及已知的顺式玉米素 (2a) 在烟草愈伤组织和生菜种子发芽生物测定中进行了细胞分裂素活性测试。在这两种生物测定中，发现细胞分裂素活性遵循 2a>2b>4b 的顺序，表明 2b 和 4b 的活性分别低于相应的反式异构体 1b 和 3b（来自丁香假单胞菌 pv savastanoi 的天然细胞分裂素）。

  DOI：

  10.1248/cpb.38.2702

文献信息

• Purines. XLV. Syntheses and cytokinin activities of the cis isomers of (1'R)-1'-methylzeatin and its 9-.BETA.-D-ribofuranoside.
  作者：Tozo FUJII、Masashi OHBA、Miwa SAKARI、Satoshi MATSUBARA

  DOI：10.1248/cpb.38.2702

  日期：——

  (1'R)-1'-Methyl-cis-zeatin (2b) and its 9-β-D-ribofuranoside (4b) have been synthesized for the first time from D-alanine (5) in 7 steps. The new cis-zeatin derivatives 2b and 4b, together with known cis-zeatin (2a), were tested for cytokinin activity in the tobacco callus and the lettuce seed germination bioassays. In both bioassays, the cytokinin activity was found to follow the order 2a>2b>4b, indicating that 2b and 4b were less active than the corresponding trans isomers 1b and 3b (natural cytokinins from Pseudomonas syringae pv savastanoi), respectively.

  (1'R)-1'-甲基-顺式玉米素 (2b) 及其 9-β-D-呋喃核苷 (4b) 首次由 D-丙氨酸 (5) 经 7 个步骤合成。新的顺式玉米素衍生物 2b 和 4b 以及已知的顺式玉米素 (2a) 在烟草愈伤组织和生菜种子发芽生物测定中进行了细胞分裂素活性测试。在这两种生物测定中，发现细胞分裂素活性遵循 2a>2b>4b 的顺序，表明 2b 和 4b 的活性分别低于相应的反式异构体 1b 和 3b（来自丁香假单胞菌 pv savastanoi 的天然细胞分裂素）。
• 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）。
• Syntheses and absolute configurations of the cytokinins 1′-methylzeatin and its 9-riboside
  作者：Taisuke Itaya、Tozo Fujii、Antonio Evidente、Giacomino Randazzo、Giuseppe Surico、Nicola S. Iacobellis

  DOI：10.1016/s0040-4039(00)87806-5

  日期：1986.1

  On the basis of the chiral syntheses of (1′R)-I and (1′S)-I and of their 9-ribosides (1″R)-III and (1″S)-III from D- and L-alanines, the structures of the cytokinins 1′-methylzeatin and its 9-riboside have been established to be (1′R)-I and (1″R)-III.

  上（1'的手性合成的基础- [R）-1和（1'小号）-I和其9- ribosides（1“ - [R）-III和（1”小号）-III从d -和大号-丙氨酸，细胞分裂素1'- methylzeatin和其9-核糖核苷的结构已经被确定为（1' - [R）-1和（1“ - [R）-III。
• FUJII, TOZO;OHBA, MASASHI;SAKARI, MIWA;MATSUBARA, SATOSHI, CHEM. AND PHARM. BULL., 38,(1990) N0, C. 2702-2706
  作者：FUJII, TOZO、OHBA, MASASHI、SAKARI, MIWA、MATSUBARA, SATOSHI

  DOI：——

  日期：——
• 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.