methyl (Z)-2-(bromomethyl)-3-cyclohexylacrylate | 204334-89-4

• 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)-3-cyclohexylacrylate
• 英文别名: methyl (Z)-2-(bromomethyl)-3-cyclohexylprop-2-enoate
• CAS: 204334-89-4
• 化学式: C₁₁H₁₇BrO₂
• 分子量: 261.159
• InChiKey: MPEMRVYTZMEHEU-JXMROGBWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 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)-3-cyclohexylacrylate 在 咪唑 、 indium 、 N-溴代丁二酰亚胺(NBS) 、 二异丁基氢化铝 、 对甲苯磺酸 、 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 (2S,5S)-2-cyclohexyl-6-methyl-3-methylideneheptane-1,5-diol
  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：

  3-环己基-3-羟基-2-亚甲基戊酸甲酯 在 N-溴代丁二酰亚胺(NBS) 、 二甲基硫 作用下， 以 二氯甲烷 为溶剂， 以82%的产率得到methyl (Z)-2-(bromomethyl)-3-cyclohexylacrylate
  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

文献信息

• Factors influencing the cytotoxicity of α-methylene-γ-hydroxy esters against pancreatic cancer
  作者：P. Veeraraghavan Ramachandran、Matthew A. Helppi、Arlie L. Lehmkuhler、Jennifer M. Marchi、C. Max Schmidt、Michele T. Yip-Schneider

  DOI：10.1016/j.bmcl.2015.07.087

  日期：2015.10

  A systematic study to identify the factors influencing the cytotoxicity of a-methylene-c-hydroxy esters against three pancreatic cancer cell lines (Panc-1, MIA-PaCa-2, and BxPC-3) has established that, in addition to Michael acceptor abilities, the possibility to lactonize to alpha-methylene-gamma-butyrolactones is as important. The substitution pattern and the number of carbons between the hydroxy and ester moieties also influence the bio-activity. (C) 2015 Elsevier Ltd. All rights reserved.
• 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.