7-allyl-6-(tert-butyldimethylsilanyloxy)-1-(3-phenylallyl)-(2S,3,3aR,6S,7S,7aR)-hexahydro-1H-indole-2-carboxylic acid methoxymethyl amide | 828921-41-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 7-allyl-6-(tert-butyldimethylsilanyloxy)-1-(3-phenylallyl)-(2S,3,3aR,6S,7S,7aR)-hexahydro-1H-indole-2-carboxylic acid methoxymethyl amide
• 英文别名: (2S,3aR,6R,7S,7aS)-6-[tert-butyl(dimethyl)silyl]oxy-N-methoxy-N-methyl-1-[(E)-3-phenylprop-2-enyl]-7-prop-2-enyl-2,3,3a,6,7,7a-hexahydroindole-2-carboxamide
• CAS: 828921-41-1
• 化学式: C₂₉H₄₄N₂O₃Si
• 分子量: 496.765
• InChiKey: YKXDNVQFDGOVBT-BPHVONKGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.93
• 重原子数：
  35
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  42
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  7-allyl-6-(tert-butyldimethylsilanyloxy)-1-(3-phenylallyl)-(2S,3,3aR,6S,7S,7aR)-hexahydro-1H-indole-2-carboxylic acid methoxymethyl amide 在 萘 、 lithium 、 L-Selectride 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 39.08h， 生成 (5S)-[7-allyl-6-hydroxy-1-(3-phenylallyl)-(2S,3,3aR,6S,7S,7aR)-hexahydro-1H-indol-2-yl]-3-methyldihydrofuran-2-one
  参考文献：
  名称：

  Asymmetric Total Syntheses of Tuberostemonine, Didehydrotuberostemonine, and 13-Epituberostemonine

  摘要：

  Detailed experimental approaches toward the pentacyclic Stemona alkaloids tuberostemonine and didehydrotuberostemonine and the close analogue 13-epituberostemonine are described. The syntheses originate with a hydroindolinone derivative that can be obtained on a large scale in a single step from carbobenzoxy-protected L-tyrosine. Highlights of the conversion of this hydroindolinone to the target structures are the three-fold use of ruthenium catalysts, first in azepine ring-closing metathesis and then in alkene isomerization and cross-metathesis propenyl-vinyl exchange, as well as the stereoselective attachment of a y-butyrolactone ring to a tetracycle core structure by use of a lithiated asymmetric bicyclo[3.2.1]octane (ABO) ortho ester. Structural analysis by density functional theory (DFT) methods revealed that the ease of oxidation of the natural product is likely due to the conformational preferences of the pyrrolidine and the fused cyclohexane rings.

  DOI：

  10.1021/ja044280k
• 作为产物：
  描述：

  (2S,3aR,7aR)-3a-hydroxy-6-oxo-2,3,3a,6,7,7a-hexahydroindole-1,2-dicarboxylic acid 1-benzyl ester 2-methyl ester 在 甲酸 吡啶 、 咪唑 、 三乙基硅烷 、 4-二甲氨基吡啶 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 sodium tetrahydroborate 、 cerium(III) chloride 、 四丙基高钌酸铵 、 四丁基氟化铵 、 palladium diacetate 、 二甲基氯化铝 、 双(三甲基硅烷基)氨基钾 、 potassium carbonate 、 N-甲基吗啉氧化物 、 三乙胺 、 三苄基膦 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 142.08h， 生成 7-allyl-6-(tert-butyldimethylsilanyloxy)-1-(3-phenylallyl)-(2S,3,3aR,6S,7S,7aR)-hexahydro-1H-indole-2-carboxylic acid methoxymethyl amide
  参考文献：
  名称：

  Asymmetric Total Syntheses of Tuberostemonine, Didehydrotuberostemonine, and 13-Epituberostemonine

  摘要：

  Detailed experimental approaches toward the pentacyclic Stemona alkaloids tuberostemonine and didehydrotuberostemonine and the close analogue 13-epituberostemonine are described. The syntheses originate with a hydroindolinone derivative that can be obtained on a large scale in a single step from carbobenzoxy-protected L-tyrosine. Highlights of the conversion of this hydroindolinone to the target structures are the three-fold use of ruthenium catalysts, first in azepine ring-closing metathesis and then in alkene isomerization and cross-metathesis propenyl-vinyl exchange, as well as the stereoselective attachment of a y-butyrolactone ring to a tetracycle core structure by use of a lithiated asymmetric bicyclo[3.2.1]octane (ABO) ortho ester. Structural analysis by density functional theory (DFT) methods revealed that the ease of oxidation of the natural product is likely due to the conformational preferences of the pyrrolidine and the fused cyclohexane rings.

  DOI：

  10.1021/ja044280k

文献信息

• Asymmetric Total Syntheses of Tuberostemonine, Didehydrotuberostemonine, and 13-Epituberostemonine
  作者：Peter Wipf、Stacey R. Spencer

  DOI：10.1021/ja044280k

  日期：2005.1.1

  Detailed experimental approaches toward the pentacyclic Stemona alkaloids tuberostemonine and didehydrotuberostemonine and the close analogue 13-epituberostemonine are described. The syntheses originate with a hydroindolinone derivative that can be obtained on a large scale in a single step from carbobenzoxy-protected L-tyrosine. Highlights of the conversion of this hydroindolinone to the target structures are the three-fold use of ruthenium catalysts, first in azepine ring-closing metathesis and then in alkene isomerization and cross-metathesis propenyl-vinyl exchange, as well as the stereoselective attachment of a y-butyrolactone ring to a tetracycle core structure by use of a lithiated asymmetric bicyclo[3.2.1]octane (ABO) ortho ester. Structural analysis by density functional theory (DFT) methods revealed that the ease of oxidation of the natural product is likely due to the conformational preferences of the pyrrolidine and the fused cyclohexane rings.