methyl endo/exo-3-(bicyclo<2,2,1>hept-5-en-2-yl)-3-oxopropanoate | 37734-07-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: methyl endo/exo-3-(bicyclo<2,2,1>hept-5-en-2-yl)-3-oxopropanoate
• 英文别名: methyl β-oxobicyclo<2.2.1>hept-5-ene-2-propanoate；Methyl 3-{bicyclo[2.2.1]hept-5-en-2-yl}-3-oxopropanoate；methyl 3-(2-bicyclo[2.2.1]hept-5-enyl)-3-oxopropanoate
• CAS: 37734-07-9
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: VIQZCXTYOYMBSX-UHFFFAOYSA-N

物化性质

• 沸点：
  71 °C(Press: 0.2 Torr)
• 密度：
  1.168±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl endo/exo-3-(bicyclo<2,2,1>hept-5-en-2-yl)-3-oxopropanoate 在 palladium on activated charcoal 盐酸 、 sodium tetrahydroborate 、 1,4-diazabicyclo[5.4.0]-7-undecene 、 硫酸 、 氢气 作用下， 以 甲醇 为溶剂， 540.0 ℃ 、101.33 kPa 条件下， 反应 44.33h， 生成 BETA-育亨宾
  参考文献：
  名称：

  Total syntheses of yohimbe alkaloids, with stereoselection for the normal, allo, and 3-epiallo series, based on annelations of 4-methoxy-1,2-dihydropyridones

  摘要：

  N-[2-(1H-3-indolyl)ethyl]-2,3-dihydro-4-pyridone (31) was generated in two steps (77% yield) from tryptamine and N-methyl-4-piperidone methiodide. Its cyclization (90% yield) and oxidation (91% yield) provided the tetracyclic analogue 32. O-Methylation and Robinson-type annelation of these vinylogous lactams (the latter in form of its N(a)-carbamate) furnished the dienones 38 (64%) and 43 (90%). Further elaboration by cyclization and/or reduction reactions selectively provided the 15,16-didehydroyohimbinones 7 or 44. Their reductions then led to yohimbinone (52, 20% overall yield from tryptamine), alloyohimbinone (11, 19% overall yield), and 3-epi-alloyohimbinone (10, 23% overall yield), which led to yohimbine (3), beta-yohimbine (9), 3-epi-alloyohimbine (53), and 3-epi-17-epi-alloyohimbine (54).

  DOI：

  10.1021/jo00008a025
• 作为产物：
  描述：

  2-乙酰基-5-降冰片烯 、 碳酸二甲酯 在 sodium hydride 作用下， 以 乙二醇二甲醚 为溶剂， 生成 methyl endo/exo-3-(bicyclo<2,2,1>hept-5-en-2-yl)-3-oxopropanoate
  参考文献：
  名称：

  丙烯酰乙酸酯及其同系物的一般合成。

  摘要：

  DOI：

  10.1016/s0040-4039(01)84925-x

文献信息

• The structure and function of oestrogens. III. 3,17β-Dihydroxy-6-oxaoestra-1,3,5(10),8(9)-tetraen-7-one and related steroidal coumarins
  作者：AS Caselli、DJ Collins、GM Stone

  DOI：10.1071/ch9820799

  日期：——

  A Pechmann condensation of resorcinol, or resorcinol monomethyl ether with ethyl t-7a-methyl- 1,5-dioxo-r-3a,4,5,6,7,7a-hexahydroindan-c-4-carboxylate (10b) gave 3-hydroxy-6-oxaoestra- 1,3,5(10),8(9)-tetraene-7,17-dione (3a), or the corresponding 3-methoxy compound (3b), respectively. Reduction of 3-hydroxy-6-oxaoestra-1,3,5(10),8(9)-tetraene-7,17-dione (3a) with sodium borohydride gave 3,17β-dihydroxy-6-oxaoestra-1,3,5(10),8(9)-tetraen-7-one (11). Compounds (3a) and (11) were tested for oestrogenic activity.

  间苯二酚或间苯二酚单甲醚与 间苯二酚或间苯二酚单甲醚与 t-7a-甲基-1,5-二氧代-r-3a,4,5,6,7,7a-六氢茚满-c-4-羧酸乙酯（10b）的 Pemann 缩合反应 (10b) 得到 3-羟基-6-氧代雌甾-1,3,5(10),8(9)-四烯-7,17-二酮 (3a)，或 或相应的 3-甲氧基化合物 (3b)。还原 用硼氢化钠还原 3-羟基-6-氧代雌甾-1,3,5(10),8(9)-四烯-7,17-二酮 (3a) 硼氢化钠还原出 3,17β-二羟基-6-氧代雌甾-1,3,5(10),8(9)-四烯-7-酮 (11)。 (11).对化合物 (3a) 和 (11) 进行了雌激素活性测试。
• US5659070A
  申请人：——

  公开号：US5659070A

  公开（公告）日：1997-08-19
• A general synthesis of esters of acryloyl acetic acid and their homologs.
  作者：Gilbert Stork、R.Nath Guthikonda

  DOI：10.1016/s0040-4039(01)84925-x

  日期：1972.1
• Total syntheses of yohimbe alkaloids, with stereoselection for the normal, allo, and 3-epiallo series, based on annelations of 4-methoxy-1,2-dihydropyridones
  作者：Martin E. Kuehne、Randy S. Muth

  DOI：10.1021/jo00008a025

  日期：1991.4

  N-[2-(1H-3-indolyl)ethyl]-2,3-dihydro-4-pyridone (31) was generated in two steps (77% yield) from tryptamine and N-methyl-4-piperidone methiodide. Its cyclization (90% yield) and oxidation (91% yield) provided the tetracyclic analogue 32. O-Methylation and Robinson-type annelation of these vinylogous lactams (the latter in form of its N(a)-carbamate) furnished the dienones 38 (64%) and 43 (90%). Further elaboration by cyclization and/or reduction reactions selectively provided the 15,16-didehydroyohimbinones 7 or 44. Their reductions then led to yohimbinone (52, 20% overall yield from tryptamine), alloyohimbinone (11, 19% overall yield), and 3-epi-alloyohimbinone (10, 23% overall yield), which led to yohimbine (3), beta-yohimbine (9), 3-epi-alloyohimbine (53), and 3-epi-17-epi-alloyohimbine (54).