(3aR,5R,7aR)-5-[tert-butyl(dimethyl)silyl]oxy-7a-methyl-3,3a,4,5,6,7-hexahydro-1-benzofuran-2-one | 171201-46-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: (3aR,5R,7aR)-5-[tert-butyl(dimethyl)silyl]oxy-7a-methyl-3,3a,4,5,6,7-hexahydro-1-benzofuran-2-one
• CAS: 171201-46-0
• 化学式: C₁₅H₂₈O₃Si
• 分子量: 284.471
• InChiKey: BNBUEKQCGBBQMR-LALPHHSUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.88
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3aR,5R,7aR)-5-[tert-butyl(dimethyl)silyl]oxy-7a-methyl-3,3a,4,5,6,7-hexahydro-1-benzofuran-2-one 在 rhodium(III) chloride 吡啶 、 六甲基磷酰三胺 、 4-二甲氨基吡啶 、 四丁基氟化铵 、 sodium hydride 、 臭氧 、 三氟乙酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 47.0h， 生成 (1'R,4'S,6'R,7'R,E)-3-methyl-5-(1'-methyl-8'-oxo-9'-oxatricyclo[4.3.0.0^4,7]non-7'-yl)methylene-3-pyrrolin-2-one
  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+
• 作为产物：
  描述：

  (+)-(1R,5R)-5-Isopropenyl-2-methylcyclohex-2-enylacetic acid 在 咪唑 、 甲醇 、 N-溴代丁二酰亚胺(NBS) 、 二甲基硫 、 偶氮二异丁腈 、 三正丁基氢锡 、 sodium methylate 、 碳酸氢钠 、 臭氧 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 67.0h， 生成 (3aR,5R,7aR)-5-[tert-butyl(dimethyl)silyl]oxy-7a-methyl-3,3a,4,5,6,7-hexahydro-1-benzofuran-2-one
  参考文献：
  名称：

  Novel stereocontrolled synthesis of the tricyclic lactone (1R,3R,6R,9S)-6,9-dimethyl-8-oxo-7-oxatricyclo[4.3.0.03,9]nonane

  摘要：

  The stereocontrolled synthesis of (1R,3R,6R,9S)-6,9-dimethyl-s-oxo-7-oxatricyclo[4.3.0.0(3,9)]nonane 1 from (R)-(-)-carvone has been accomplished by application of a 13-step sequence with 12% overall yield. The absolute stereochemistry of the unsaturated acid 8a has been established by X-ray analysis of the chiral amide 8c. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(97)00641-1

文献信息

• Synthetic studies towards (+)-Dihydroampullicin. Michael addition of N-Boc-2-(tert-butyldimethylsiloxy)-3-methyl-pyrrole to α-methylene lactones
  作者：Isabel Marcos、Elena Redero、Francisco Bermejo

  DOI：10.1016/s0040-4039(00)01499-4

  日期：2000.10

  N-(tert-butoxycarbonyl)-2-(tert-butyldimethylsiloxy)-3-methyl-pyrrole (4) to several α-methylene lactones catalyzed by fluoride ions yielded the corresponding homologated products (26–30) with good yields. Application of this reaction to the sililoxy bicyclic lactone (5) allowed us to isolate the tricyclic lactone (26), a highly valuable intermediate in our synthetic strategy leading to the growth

  的迈克尔加成ñ - （叔丁氧羰基）-2-（叔甲基甲硅烷氧基）-3-甲基吡咯（4）由氟离子催化的几个α亚甲基内酯得到相应的同系化的产品（26 - 30）具有良好的产量。该反应在甲硅烷氧​​基双环内酯（5）上的应用使我们能够分离出三环内酯（26），这是我们合成策略中非常有价值的中间体，可导致生长调节剂（+）-二氢氨苄青霉素（1）。
• 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.
• Novel stereocontrolled synthesis of the tricyclic lactone (1R,3R,6R,9S)-6,9-dimethyl-8-oxo-7-oxatricyclo[4.3.0.03,9]nonane
  作者：Rosario Rico、Julián Zapico、Francisco Bermejo、S.Bamidele Sanni、Santiago Garcı́a-Granda

  DOI：10.1016/s0957-4166(97)00641-1

  日期：1998.1

  The stereocontrolled synthesis of (1R,3R,6R,9S)-6,9-dimethyl-s-oxo-7-oxatricyclo[4.3.0.0(3,9)]nonane 1 from (R)-(-)-carvone has been accomplished by application of a 13-step sequence with 12% overall yield. The absolute stereochemistry of the unsaturated acid 8a has been established by X-ray analysis of the chiral amide 8c. (C) 1998 Elsevier Science Ltd. All rights reserved.
• 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.