(1-tert-butoxycarbonyl-3-methyl-3-pyrrolin)-5-yl-phosphonic acid diethyl ester | 181635-62-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯啉
• 英文名称: (1-tert-butoxycarbonyl-3-methyl-3-pyrrolin)-5-yl-phosphonic acid diethyl ester
• 英文别名: tert-butyl 2-diethoxyphosphoryl-4-methyl-5-oxo-2H-pyrrole-1-carboxylate
• CAS: 181635-62-1
• 化学式: C₁₄H₂₄NO₆P
• 分子量: 333.321
• InChiKey: XPXWDFCJPNYTDN-UHFFFAOYSA-N

物化性质

• 沸点：
  413.8±55.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  82.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (1-tert-butoxycarbonyl-3-methyl-3-pyrrolin)-5-yl-phosphonic acid diethyl ester 在 碘 、 sodium hydride 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 为溶剂， 反应 8.5h， 生成 (1'R,4'S,6'R,7'R,Z)-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：

  3-甲基-2-吡咯烷酮 在 4-二甲氨基吡啶 、 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 、 溶剂黄146 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 四氯化碳 、 正己烷 为溶剂， 反应 10.5h， 生成 (1-tert-butoxycarbonyl-3-methyl-3-pyrrolin)-5-yl-phosphonic acid diethyl ester
  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

• Stereoselective preparation of (5E)- and (5Z)-5-benzylidene-3-methyl-3-pyrrolin-2-ones. Application to the synthesis of ampullicine and isoampullicine
  作者：Rosario Rico、Francisco Bermejo

  DOI：10.1016/0040-4039(96)01232-4

  日期：1996.8

  The application of N-Boc-5-phosphoranylidene- and N-Boc-5-diethylphosphonate-3-methyl-3-pyrrolin-2-ones to the stereoselective synthesis of (5E)- and (5Z)-3-methyl-5-benzylidene-3-pyrrolin-2-ones is examined. The stereoselective synthesis of the growth regulators Ampullicin and Isoampullicin by using both Wittig intermediates has also been achieved.

  N-Boc-5-膦基亚烷基-和N-Boc-5-二乙基膦酸酯-3-甲基-3-吡咯啉-2-酮在（5E）-和（5Z）-3-甲基-5的立体选择性合成中的应用检查了-亚苄基-3-吡咯啉-2-酮。还已经通过使用两种Wittig中间体实现了生长调节剂Ampullicin和Isoampullicin的立体选择性合成。
• Synthesis of azaspiro[4.5]decane systems by oxidative cyclization of olefinic precursors
  作者：María J. Martín-López、Francisco Bermejo

  DOI：10.1016/s0040-4020(98)00746-7

  日期：1998.10

  The synthesis of 6-benzyloxycarbonyl-1-oxa-6-azaspiro[4.5]decan-2-one (17) and 6-benzyloxycarbonyl-1,6-diazaspiro[4.5]decan-2-one (18) from the D,L-pipecolic acid derivative 10, is described. The synthesis of (±)-6-benzyl-3-methyl-1,6-diazaspiro[4.5]dec-3-ene-2,7-dione (29), the spiro structural unit of (±)-pandamarine (8) has been achieved by oxidative cylization of the (Z) and (E) isomers of 5-(N-

  由D，合成6-苄氧基羰基-1-氧杂-6-氮杂螺[4.5]癸-2-（17）和6-苄氧基羰基-1,6-二氮杂螺[4.5]癸-2-（18），描述了L-哌酸衍生物10。（±）-6-苄基-3-甲基-1,6-二氮杂螺[4.5] dec-3-ene-2,7-二酮（29）（（±）-pandamarine的螺结构单元）的合成（8）已通过氧化环化5-（N-苄基-4-羧酰胺基丁烯）-3-甲基-3-吡咯啉-2-酮（25）和（26）的（Z）和（E）异构体而实现。还讨论了分子内环化过程中获得的立体选择性。
• 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.