2-exo-Acetamidonorbornene-2-endo-carboxylic acid methyl ester | 72431-82-4

• 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-exo-Acetamidonorbornene-2-endo-carboxylic acid methyl ester
• 英文别名: 2-exo-acetamido-5-norbornene-2-endo-carboxylic acid methyl ester；methyl 2-exo-acetylamino-5-norboren-2-endo-carboxylate；methyl 2-exo-acetamidobicyclo<2.2.1>hept-5-ene-2-endo-carboxylate；(1RS,2SR,4RS)-methyl 2-acetylamino-bicyclo[2.2.1]hept-5-ene-2-carboxylate；(1R,2S,4R)-2-(Acetylamino)bicyclo[2.2.1]hepta-5-ene-2-carboxylic acid methyl ester；methyl (1R,2S,4R)-2-acetamidobicyclo[2.2.1]hept-5-ene-2-carboxylate
• CAS: 72431-82-4；72431-85-7；131150-28-2；131150-29-3；136314-92-6；136314-93-7；139237-37-9；139237-38-0
• 化学式: C₁₁H₁₅NO₃
• 分子量: 209.245
• InChiKey: RUTMULAEKSLWQD-YWVKMMECSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-exo-Acetamidonorbornene-2-endo-carboxylic acid methyl ester 在 氢氧化钾 作用下， 以 甲醇 、 水 为溶剂， 反应 4.0h， 以75%的产率得到(1R)-2-乙酰氨基双环[2.2.1]庚-5-烯-2-羧酸
  参考文献：
  名称：

  A two-step synthesis of 2-exo-substituted 2-endo-aminonorbornenes from 2-acetamidonorbornene-2-carboxylic acids

  摘要：

  2-exo-Substituted 2-endo-acetamidonorbornenes (3) were synthesized in a two-step procedure from 2-acetamidonorbornene-2-carboxylic acids (1, 1') with exceedingly high exo-selectives based on a new approach involving anodic decarboxylation followed by organoaluminum-promoted nucleophilic substitution on 2-endo-acetamido-2-exo-methoxynorbornene (2).

  DOI：

  10.1016/s0040-4020(01)87043-5
• 作为产物：
  描述：

  (1R,2S,4R)-2-exo-acetamidobicyclo<2.2.1>hept-5-ene-2-endo-carboxylate of (-)-cis-3-hydroxy isobornyl neopentyl ether 在 氢氧化钾 作用下， 以 甲醇 、 乙醚 、 乙醇 为溶剂， 反应 48.0h， 生成 2-exo-Acetamidonorbornene-2-endo-carboxylic acid methyl ester
  参考文献：
  名称：

  Asymmetric synthesis of 2-exo-aminonorbornane-2-endo-carboxylic acid derivatives

  摘要：

  The Diels-Alder reaction of cyclopentadiene with N-acetyl-alpha,beta-didehydroalaninate of (-)-cis-3-hydroxy isobornyl neopentyl ether yields the corresponding 2-endo(exo)-acetamido-5-norbornene-2-exo(endo)-carboxylates with total diastereofacial selectivity and with a preference for the cycloadduct with the ester group placed at the endo position. So this dienophile is complementary with the previously described (-)-menthyl N-acetyl-alpha,beta-didehydroalaninate for the asymmetric synthesis of 2-aminonorbornane-2-carboxylic acids, since with the latter dienophile exo cycloadducts are preferably obtained with a high diastereofacial selectivity.

  DOI：

  10.1016/s0957-4166(00)82170-9

文献信息

• Syntheses and Antiulcer Activities of 2-Aminonorbornene Derivatives.
  作者：Hiroyoshi YAMAZAKI、Hiroshi HORIKAWA、Takashi NISHITANI、Tameo IWASAKI、Kunio NOSAKA、Hajime TAMAKI

  DOI：10.1248/cpb.40.102

  日期：——

  2, 2, -Disubstituted norbornenes (1, 2), 2, 2-Disubstituted norbornane (3), 2, 2, 3-trisubstituted norbornenes (4, 5), oxanorbornenes (6) and azanorbornenes (7) were synthesized by the Diels-Alder reaction using α, β-dehydroamino acids as a key step, and their antiulcer activities were examined. The oxazolidine derivative (1h) exhibited the most potent activities against several ulcer-models in rat.

  以α，β-脱氢氨基酸为关键步骤，通过 Diels-Alder 反应合成了 2，2，-二取代降冰片烯（1，2）、2，2-二取代降冰片烷（3）、2，2，3-三取代降冰片烯（4，5）、氧杂降冰片烯（6）和氮杂降冰片烯（7），并考察了它们的抗溃疡活性。恶唑烷衍生物（1h）对大鼠的几种溃疡模型表现出最有效的活性。
• A synthesis of 2-endo-amino-2-exo-hydroxymethylnorbornenes having inhibitory activity against protein kinase C.
  作者：Tameo IWASAKI、Hiroyoshi YAMAZAKI、Takashi NISHITANI、Tadashi SATO

  DOI：10.1248/cpb.39.527

  日期：——

  2-endo-Hexadecylamino-2-exo-hydroxymethylnorbornene (1a) was synthesized from 2-acetamidonorbornene-2-carboxylic acid methyl ester (2) in a good overall yield. 2-endo-Hexadecylamino-2, 3-exo-bis(hydroxymethyl)norbornene (1b) was synthesized starting from dimethyl acetamidofumarate based on Diels-Alder strategy. 1a and 1b inhibited protein kinase C at the IC50 values of 2×10-5M and 1×10-5M, respectively, but not protein kinase A at a concentration of 1×10-3M. The structure-activity relationships are discussed.

  2-endo-Hexadecylamino-2-exo-hydroxymethylnorbornene (1a) 由 2-acetamidonorbornene-2-carboxylic acid methyl ester (2) 合成，总收率良好。2-endo-Hexadecylamino-2, 3-exo-bis(hydroxymethyl)norbornene (1b) 是基于 Diels-Alder 策略从乙酰氨基富马酸二甲酯开始合成的。1a 和 1b 对蛋白激酶 C 的抑制作用 IC50 值分别为 2×10-5M 和 1×10-5M，而对蛋白激酶 A 的抑制作用 IC50 值为 1×10-3M。本文讨论了结构-活性关系。
• The use of heterogeneous catalysis in Diels-Alder reactions of N-acetyl-α,β-dehydroalaninates
  作者：Carlos Cativiela、JoséI. García、JoséA. Mayoral、Elisabet Pires、Ana J. Royo、François Figueras

  DOI：10.1016/0040-4020(94)01008-n

  日期：1995.1

  Several solids have been tested as heterogeneous catalysts in the Diels-Alder reactions of the relatively unreactive dienophiles methyl (1a) and (−)-menthyl (1b) α,β-dehydroalaninates with cyclopentadiene, which is the key step in the asymmetric synthesis of cycloaliphatic α-amino acids. Reactions were carried out in toluene and in the absence of a solvent, the latter method leading to higher percentages

  在相对不活泼的亲二烯体甲基（1a）和（-）-薄荷基（1b）α，β-脱氢丙氨酸与环戊二烯的Diels-Alder反应中，已经测试了几种固体作为非均相催化剂，这是不对称合成环戊二烯的关键步骤脂环族α-氨基酸。反应在甲苯中和在没有溶剂的情况下进行，后一种方法导致较高的转化率。用路易斯酸改性的硅胶是非手性亲二烯体1a反应的最佳催化剂，但由于扩散限制，它们在手性亲二烯体1b的反应中完全无效。在手性亲双烯体1b的情况下，硅胶是最好的催化剂。两个外型/内型和diastereofacial选择性是非常类似于使用均相催化剂获得的那些。在外环加合物中获得的完全非对映选择性构成了迄今为止在与非均相催化剂进行的不对称Diels-Alder反应中描述的最佳不对称诱导。
• Asymmetric synthesis of cycloaliphatic α-amino acids with a norbornane skeleton
  作者：Carlos Cativiela、Pilar López、JoséA. Mayoral

  DOI：10.1016/0957-4166(90)90038-c

  日期：1990.1

  The asymmetric synthesis of endo and exo 2-aminonorbornane-2-carboxylic acids is carried out via the Diels-Alder reaction between cyclopentadiene and (−)-menthyl N-acetyl-α,β-dehydroalaninate. It is shown that this dienophile is more reactive than the corresponding methyl ester, which opens the way for the use of chiral N-acetyl-α,β-dehydroalaninates as dienophiles in asymmetric Diels-Alder reactions

  内和外2-氨基降冰片烷-2-羧酸的不对称合成是通过环戊二烯与（-）-薄荷基N-乙酰基-α，β-脱氢丙氨酸盐之间的狄尔斯-阿尔德反应进行的。结果表明，该亲二烯体比相应的甲酯更具反应性，这为在不对称Diels-Alder反应中将手性N-乙酰基-α，β-脱氢丙氨酸盐用作亲二烯体开辟了道路。由于以前认为中等的手性助剂具有很高的非对面选择性，因此乙酰胺基必须发挥重要作用，对此进行了讨论。
• A synthesis of 2-aminonorbornene-2-carboxylic acid derivatives by diels-alder reaction using α,β-dehydroalaninates as a dienophile
  作者：Hiroshi Horikawa、Takashi Nishitani、Tameo Iwasaki、Yoshitaka Mushika、Ichizo Inoue、Muneji Miyoshi

  DOI：10.1016/0040-4039(80)88077-4

  日期：1980.1

  The Diels-Alder reaction of N-acyl-α,β-dehydroalanine esters with cyclopentadiene afforded a mixture of the stereoisomers of acylaminonorbornene-2-carboxylic acid esters in good yields.

  N-酰基-α，β-脱氢丙氨酸酯与环戊二烯的狄尔斯-阿尔德反应以良好的产率提供了酰基氨基降冰片烯-2-羧酸酯的立体异构体的混合物。