methyl 4α-carboxy-3β,13α-dihydroxy-4β-methyl-16-methylenegibb-1-ene-6β-carboxylate | 62486-69-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl 4α-carboxy-3β,13α-dihydroxy-4β-methyl-16-methylenegibb-1-ene-6β-carboxylate
• 英文别名: Hydrogeno I；2β,7-dihydroxy-1-methyl-8-methylene-7β-gibb-4-ene-1α,10β-dicarboxylic acid-10-methyl ester；2β,7-Dihydroxy-1-methyl-8-methylen-7β-gibb-4-en-1α,10β-dicarbonsaeure-10-methylester；(1S,2S,3S,4S,5S,9R,12S)-5,12-dihydroxy-2-methoxycarbonyl-4-methyl-13-methylidenetetracyclo[10.2.1.01,9.03,8]pentadec-7-ene-4-carboxylic acid
• CAS: 62486-69-5
• 化学式: C₂₀H₂₆O₆
• 分子量: 362.423
• InChiKey: QWVAVLNJMKTOCF-SYMNSWBZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  104
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 4α-carboxy-3β,13α-dihydroxy-4β-methyl-16-methylenegibb-1-ene-6β-carboxylate 在 sodium tetrahydroborate 、 草酰氯 、 对甲苯磺酸 、 N,N-二甲基甲酰胺 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 5.0h， 生成 ent-3α,13-diacetoxy-19-hydroxy-20-norgibberell-1(10),16-dien-7-oic acid, 7-methyl ester
  参考文献：
  名称：

  Synthesis, stability and biological activity of 19-desoxy-gibberellins A1 and A3

  摘要：

  The synthetic conversion of gibberellin A3 (GA3) to the 19-desoxy-derivatives of GA1 and GA3 is described. The key steps involve regiospecific reduction of the known GA3 hydrogenolysis product at the C-19 carboxyl group via treatment of the acyl chloride with zinc borohydride, followed by an iodocyclization of the resultant alcohol. 19-Desoxy-GA1 and GA3 are stable in alkali, unlike their parent lactones GA1 and GA3. Both derivatives are biologically active in inducing alpha-amylase production in protoplasts of Avena fatua aleurone. They have biological activities of one order of magnitude less than that of the natural analogues. These data reveal the significant contribution of the lactone carbonyl to the observed response (receptor affinity) of GA1 and GA3.

  DOI：

  10.1016/0031-9422(91)80004-k
• 作为产物：
  描述：

  赤霉素 在 sodium tetrahydroborate 、 nickel dichloride 作用下， 以 甲醇 为溶剂， 反应 7.0h， 生成 methyl 4α-carboxy-3β,13α-dihydroxy-4β-methyl-16-methylenegibb-1-ene-6β-carboxylate
  参考文献：
  名称：

  3-羟基-Δ1.10-12,16-环赤霉素12二甲酯的简明合成——粗枝赤霉素类似物

  摘要：

  摘要 本文描述了从赤霉素酸 GA3 3 化学合成粗纤维赤霉素类似物 - 3-羟基-δ1.10-12, 16-环赤霉素二甲酯 4。关键步骤是分解甲苯磺酰腙 11 以构建新型 [3.2.1.0.2.7] 辛烷系统。

  DOI：

  10.1080/00397919508011482

文献信息

• The synthesis of 1 -methyl- and 1α,2α-methylene-gibberellins
  作者：Jake MacMillan、Christine L. Willis

  DOI：10.1039/p19850002177

  日期：——

  enone with sodium borohydride gave 1α-methylGA4methyl ester, which was hydrolysed to 1α-methylGA4, and 1α-methyl-3-epi-GA4, methyl ester which was deoxygenated to give 1α-methylG9. The palladium-catalysed reduction of the 1-methyl enone gave 1β-methylGA4-3-ketone and 1α-methylGA4-3-ketone which were converted into the corresponding 1β-methylGA4 and 1α-methylGA4. The analogous synthesis of the C-l alkylated

  描述了进一步研究结构-生物学活性关系所需的1α-甲基-，1β-甲基-和1α，2α-亚甲基-赤霉素的合成。衍生自GA 7 -3-酮-7-甲酯的吡唑啉的热解反应得到主要产物相应的1-甲基烯酮和少量的1α，2α-亚甲基GA 4 -3-酮-7-甲酯。将后一化合物还原并水解为1α，2α-亚甲基GA 4。用硼氢化钠还原1-甲基烯酮，得到1α-甲基GA 4甲酯，将其水解为1α-甲基GA 4；将1α-甲基-3 - epi -GA 4，经脱氧反应，得到1α-甲基G9。钯催化的1-甲基烯酮的还原得到1β-甲基GA 4 -3-酮和1α-甲基GA 4 -3-酮，它们被转化为相应的1β-甲基GA 4和1α-甲基GA 4。的Cl组成的类似合成烷基化的13羟基化的赤霉素是通过使用苯甲酰甲基酯的改进，以保护C-7，从而提供路由1β-methylGA 1，1α-methylGA 1，和1α，2α-methyleneGA 1。
• 487. Gibberellic acid. Part XXV. Some new reduction products of gibberellic acid and its methyl ester
  作者：T. P. C. Mulholland

  DOI：10.1039/jr9630002606

  日期：——
• Grove et al., Journal of the Chemical Society, 1958, p. 1236,1239
  作者：Grove et al.

  DOI：——

  日期：——
• Concise Synthesis of 3-Hydroxy-Δ^1.10−12,16-cyclogibberellin 12 Dimethyl Ester—A Trachylobagibberellin Analogue
  作者：Xiaodong Nie、Wenge Xie、Gang Lin、Maosen Song、Xinfu Pan

  DOI：10.1080/00397919508011482

  日期：1995.12

  Abstract Chemical synthesis of a trachylobagibberellin analogue - 3-hydroxy- δ1.10−12, 16-cyclogibberellin dimethyl ester 4 from gibberellin acid GA3 3 was described herein. The key step is the decomposition of the tosylhydrazone 11 to construct the novel [3.2.1.0.2.7] octane system.

  摘要 本文描述了从赤霉素酸 GA3 3 化学合成粗纤维赤霉素类似物 - 3-羟基-δ1.10-12, 16-环赤霉素二甲酯 4。关键步骤是分解甲苯磺酰腙 11 以构建新型 [3.2.1.0.2.7] 辛烷系统。
• Synthesis, stability and biological activity of 19-desoxy-gibberellins A1 and A3
  作者：Jane L. Ward、Gary J. Reynolds、Richard Hooley、Michael H. Beale

  DOI：10.1016/0031-9422(91)80004-k

  日期：1993.11

  The synthetic conversion of gibberellin A3 (GA3) to the 19-desoxy-derivatives of GA1 and GA3 is described. The key steps involve regiospecific reduction of the known GA3 hydrogenolysis product at the C-19 carboxyl group via treatment of the acyl chloride with zinc borohydride, followed by an iodocyclization of the resultant alcohol. 19-Desoxy-GA1 and GA3 are stable in alkali, unlike their parent lactones GA1 and GA3. Both derivatives are biologically active in inducing alpha-amylase production in protoplasts of Avena fatua aleurone. They have biological activities of one order of magnitude less than that of the natural analogues. These data reveal the significant contribution of the lactone carbonyl to the observed response (receptor affinity) of GA1 and GA3.