methyl (Z)-2-(bromomethyl)-4-methylpent-2-enoate | 137104-39-3

• 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 (Z)-2-(bromomethyl)-4-methylpent-2-enoate
• CAS: 137104-39-3
• 化学式: C₈H₁₃BrO₂
• 分子量: 221.094
• InChiKey: BNOKKUZTVFYPGJ-QPJJXVBHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl (Z)-2-(bromomethyl)-4-methylpent-2-enoate 在 咪唑 、 4-二甲氨基吡啶 、 indium 、 N-溴代丁二酰亚胺(NBS) 、 二异丁基氢化铝 、 对甲苯磺酸 、 三乙胺 、 对甲苯磺酰氯 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 42.0h， 生成 (2R,5R)-4-methylidene-2-phenyl-5-propan-2-yloxane
  参考文献：
  名称：

  Effective 1,4-Asymmetric C−C/C−O Stereoinduction in Indium-Promoted Coupling Reactions of Aldehydes to Protected and Unprotected [1-(Bromomethyl)vinyl] Alkanols. The Status of Intramolecular Chelation within Functionalized Allylindium Reagents

  摘要：

  The stereochemistry of the coupling reactions of oxygen-substituted bromides 8-10 with isobutyraldehyde, benzaldehyde, and cyclohexanecarboxaldehyde in water is described. The examples involving the O-silylated derivatives 8 exhibit moderate anti stereoselectivity. In contrast, rather high (most often in excess of 80:20) syn diastereofacial bias is observed when hydroxy bromides 10 are involved. Consequently, stereocontrolled 1,4-asymmetric induction under aqueous conditions can be realized in either direction on demand. These results are considered to reflect the fact that the siloxy systems enter into C-C bond formation via conventional Felkin-Anh transition state arrangements. The crossover observed for the unprotected analogues is believed to be a consequence of the preferred adoption of chelated transition states, these interactions likely being fundamental to aqueous organometallic chemistry.

  DOI：

  10.1021/jo9715534
• 作为产物：
  描述：

  methyl 3-hydroxy-4-methyl-2-methylenepentanoate 在 四溴化碳 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以97%的产率得到methyl (Z)-2-(bromomethyl)-4-methylpent-2-enoate
  参考文献：
  名称：

  使用Appel试剂（PPh 3 / CBr 4）从Baylis-Hillman加合物温和而实用的立体选择性合成（Z）-和（E）-烯丙基溴：轻度合成C和E的简便方法

  摘要：

  在室温下，Appel试剂（PPh 3 / CBr 4）已用于从Baylis-Hillman加合物中高产率地立体选择性合成（Z）-和（E）-烯丙基溴。该方法已用于合成天然存在的生物活性脂肪酸酰胺，半乳糖C和E。

  DOI：

  10.1016/j.tetlet.2009.02.132

文献信息

• Rhodium-Catalyzed Enantioselective Hydrogenation of β-Phthalimide Acrylates to Synthesis of β²-Amino Acids
  作者：Hanmin Huang、Xiongcai Liu、Jun Deng、Min Qiu、Zhuo Zheng

  DOI：10.1021/ol0612399

  日期：2006.7.1

  [Structure: see text] The enantioselective hydrogenation of beta-phthalimide acrylates provides the corresponding chiral beta2-amino acids in excellent enantiomeric excess catalyzed by Rh-monophosphorus.

  [结构：见正文]β-邻苯二甲酰亚胺丙烯酸酯的对映选择性氢化，在Rh-单磷的催化下，以优异的对映体过量提供了相应的手性β2-氨基酸。
• ?-Methylidene- and ?-Alkylidene-?-lactams from Nonproteinogenic Amino Acids
  作者：Rainer Buchholz、H. Martin R. Hoffmann

  DOI：10.1002/hlca.19910740608

  日期：1991.9.18

  Treatment of methyl 2-(1-hydroxyalkyl)prop-2-enoates 1 with conc. HBr solution afforded methyl (Z)-2-(bromomethyl)alk-2-enoates 2, which were transformed regioselectively into N-substituted methyl (E)-2- (aminomethyl)alk-2-enoates 3 (SN2 reaction) and into N-substituted methyl 2-(1-aminoalkyl)prop-2-enoates 4(SN2′ reaction). Regiocontrol of nucleophilic attack by amine was accomplished simply by choice

  用浓溶液处理2-（1-羟烷基）丙-2-烯酸甲酯1。用HBr溶液得到（Z）-2-（溴甲基）烷-2-烯酸甲酯2，将其区域​​选择性地转化成N-取代的甲基（E）-2-（氨甲基）烷-2-烯酸酯3（S N 2反应）并进入ñ取代的甲基2-（1-氨基烷基）丙-2- enoates 4（S ñ 2'反应）。胺对亲核性攻击的区域控制仅通过选择溶剂即可完成，S N 2反应发生在MeCN和S N中。在石油醚中进行2'反应。水解和内酰胺化分别得到β-内酰胺7和8，分别在C（3）处含有外环亚烷基和亚甲基。
• ALLYLINDATION IN AQUEOUS MEDIA: METHYL 3-(HYDROXYMETHYL)-4-METHYL-2-METHYLENEPENTANOATE
  作者：Bennett, George D.、Paquette, Leo A.、Dong, Yan、Wolff, Steven

  DOI：10.15227/orgsyn.077.0107

  日期：——
• Mild and practical stereoselective synthesis of (Z)- and (E)-allyl bromides from Baylis–Hillman adducts using Appel agents (PPh3/CBr4): a facile synthesis of semiplenamides C and E
  作者：Biswanath Das、Kongara Damodar、Nisith Bhunia、Boddu Shashikanth

  DOI：10.1016/j.tetlet.2009.02.132

  日期：2009.5

  Appel agents (PPh3/CBr4) have been utilized for high-yielding stereoselective synthesis of (Z)- and (E)-allyl bromides from Baylis–Hillman adducts at room temperature. The method has been applied for the synthesis of naturally occurring bioactive fatty acid amides, semiplenamides C and E.

  在室温下，Appel试剂（PPh 3 / CBr 4）已用于从Baylis-Hillman加合物中高产率地立体选择性合成（Z）-和（E）-烯丙基溴。该方法已用于合成天然存在的生物活性脂肪酸酰胺，半乳糖C和E。
• Effective 1,4-Asymmetric C−C/C−O Stereoinduction in Indium-Promoted Coupling Reactions of Aldehydes to Protected and Unprotected [1-(Bromomethyl)vinyl] Alkanols. The Status of Intramolecular Chelation within Functionalized Allylindium Reagents
  作者：Leo A. Paquette、George D. Bennett、Methvin B. Isaac、Adnan Chhatriwalla

  DOI：10.1021/jo9715534

  日期：1998.3.1

  The stereochemistry of the coupling reactions of oxygen-substituted bromides 8-10 with isobutyraldehyde, benzaldehyde, and cyclohexanecarboxaldehyde in water is described. The examples involving the O-silylated derivatives 8 exhibit moderate anti stereoselectivity. In contrast, rather high (most often in excess of 80:20) syn diastereofacial bias is observed when hydroxy bromides 10 are involved. Consequently, stereocontrolled 1,4-asymmetric induction under aqueous conditions can be realized in either direction on demand. These results are considered to reflect the fact that the siloxy systems enter into C-C bond formation via conventional Felkin-Anh transition state arrangements. The crossover observed for the unprotected analogues is believed to be a consequence of the preferred adoption of chelated transition states, these interactions likely being fundamental to aqueous organometallic chemistry.