(3R,3aR,5R,7aR)-5-(p-toluenesulfonyloxy)-7a-methyl-3-(2-propenyl)-3a,4,567,7a-hexahydro-2(3H)-benzofuranone | 171201-49-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3R,3aR,5R,7aR)-5-(p-toluenesulfonyloxy)-7a-methyl-3-(2-propenyl)-3a,4,567,7a-hexahydro-2(3H)-benzofuranone
• 英文别名: [(3R,3aR,5R,7aR)-7a-methyl-2-oxo-3-prop-2-enyl-3,3a,4,5,6,7-hexahydro-1-benzofuran-5-yl] 4-methylbenzenesulfonate
• CAS: 171201-49-3
• 化学式: C₁₉H₂₄O₅S
• 分子量: 364.463
• InChiKey: JILDLHOXQYYKPH-KLICCBINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  78
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3R,3aR,5R,7aR)-5-(p-toluenesulfonyloxy)-7a-methyl-3-(2-propenyl)-3a,4,567,7a-hexahydro-2(3H)-benzofuranone 在 六甲基磷酰三胺 、 四丁基氟化铵 、 氧气 、 三氟乙酸 、 copper(l) chloride 、 palladium dichloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 89.0h， 生成 (-)-ampullicin
  参考文献：
  名称：

  Total synthesis of (−)-ampullicin and (+)-isoampullicin two growth regulators from Ampulliferina Sp. No. 27

  摘要：

  The growth regulators (-)-Ampullicin (1) and (+)-isoampullicin (2) have been synthesized utilizing carbaldehyde (25) as the chiral source and N-tertbutoxycarbonyl-3-methyl-2-(trimethylsiloxy)pyrrole (33) as the five-carbon homologative reagent. The synthesis of (1) and (2) is discussed in the context of retrosynthetic analysis. Carbaldehyde (25), has been prepared from both enantiomers of carvone, either (7) or (9), by application of a 15-step sequence with 4.7% and 5.4% overall yields respectively.

  DOI：

  10.1016/0040-4039(95)01625-r
• 作为产物：
  描述：

  (+)-(1R,5R)-5-Isopropenyl-2-methylcyclohex-2-enylacetic acid 在 吡啶 、 咪唑 、 六甲基磷酰三胺 、 4-二甲氨基吡啶 、 N-羟基丁二酰亚胺 、 四丁基氟化铵 、 N,N'-二环己基碳二亚胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 38.0h， 生成 (3R,3aR,5R,7aR)-5-(p-toluenesulfonyloxy)-7a-methyl-3-(2-propenyl)-3a,4,567,7a-hexahydro-2(3H)-benzofuranone
  参考文献：
  名称：

  Total Synthesis of (+)-Ampullicin and (+)-Isoampullicin:  Two Fungal Metabolites with Growth Regulatory Activity Isolated from Ampulliferina Sp. 27

  摘要：

  The total synthesis of the growth regulators (+)-ampullicin 1 and (+)-isoampullicin 2 from (R)(-)-carvone 5 was accomplished by application of an 18-step sequence with 4.5% overall yield. The crucial step of the synthetic strategy lies on the internal displacement of tosylate 13 by means of the lactone enolate. In this way, access was opened to the tricyclic core present in these biologically active sesquiterpenic amides. A Horner-Emmons reaction between the carbaldehyde 16 and the phosphonate 22 led us to the stereoselective preparation of (+)-ampullicin 1. Standard transformation of I into the thermodynamically more stable geometric isomer (+)-isoampullicin 2 was trivial. The absolute configuration of both amides was established by X-ray analysis of a sample of synthetic (+)-isoampullicin 2.

  DOI：

  10.1021/jo010527+

文献信息

• Total synthesis of (−)-ampullicin and (+)-isoampullicin two growth regulators from Ampulliferina Sp. No. 27
  作者：Rosario Rico、Francisco Bermejo

  DOI：10.1016/0040-4039(95)01625-r

  日期：1995.10

  The growth regulators (-)-Ampullicin (1) and (+)-isoampullicin (2) have been synthesized utilizing carbaldehyde (25) as the chiral source and N-tertbutoxycarbonyl-3-methyl-2-(trimethylsiloxy)pyrrole (33) as the five-carbon homologative reagent. The synthesis of (1) and (2) is discussed in the context of retrosynthetic analysis. Carbaldehyde (25), has been prepared from both enantiomers of carvone, either (7) or (9), by application of a 15-step sequence with 4.7% and 5.4% overall yields respectively.
• Total Synthesis of (+)-Ampullicin and (+)-Isoampullicin:  Two Fungal Metabolites with Growth Regulatory Activity Isolated from <i>Ampulliferina</i> Sp. 27
  作者：Francisco A. Bermejo、Rosario Rico-Ferreira、S. Bamidele-Sanni、Santiago García-Granda

  DOI：10.1021/jo010527+

  日期：2001.12.1

  The total synthesis of the growth regulators (+)-ampullicin 1 and (+)-isoampullicin 2 from (R)(-)-carvone 5 was accomplished by application of an 18-step sequence with 4.5% overall yield. The crucial step of the synthetic strategy lies on the internal displacement of tosylate 13 by means of the lactone enolate. In this way, access was opened to the tricyclic core present in these biologically active sesquiterpenic amides. A Horner-Emmons reaction between the carbaldehyde 16 and the phosphonate 22 led us to the stereoselective preparation of (+)-ampullicin 1. Standard transformation of I into the thermodynamically more stable geometric isomer (+)-isoampullicin 2 was trivial. The absolute configuration of both amides was established by X-ray analysis of a sample of synthetic (+)-isoampullicin 2.