methyl 3-(3-(2-(benzyloxy)ethyl)-2-oxo-1-(2-(1-tosyl-1H-indol-3-yl)acetyl)-piperidin-3-yl)-2-diazo-3-oxopropanoate | 934586-52-4

• 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: methyl 3-(3-(2-(benzyloxy)ethyl)-2-oxo-1-(2-(1-tosyl-1H-indol-3-yl)acetyl)-piperidin-3-yl)-2-diazo-3-oxopropanoate
• 英文别名: Methyl 2-diazo-3-[1-[2-[1-(4-methylphenyl)sulfonylindol-3-yl]acetyl]-2-oxo-3-(2-phenylmethoxyethyl)piperidin-3-yl]-3-oxopropanoate；methyl 2-diazo-3-[1-[2-[1-(4-methylphenyl)sulfonylindol-3-yl]acetyl]-2-oxo-3-(2-phenylmethoxyethyl)piperidin-3-yl]-3-oxopropanoate
• CAS: 934586-52-4
• 化学式: C₃₅H₃₄N₄O₈S
• 分子量: 670.743
• InChiKey: ZCAWPACKWJMHFB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  48
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  139
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  methyl 3-(3-(2-(benzyloxy)ethyl)-2-oxo-1-(2-(1-tosyl-1H-indol-3-yl)acetyl)-piperidin-3-yl)-2-diazo-3-oxopropanoate 在 platinum(IV) oxide 、 镍 rhodium(II) acetate dimer 、 盐酸 、 tetraphosphorus decasulfide 、 六甲基二硅氧烷 、 氢气 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 31.5h， 生成 (3aS,5S,5aR,10bR,12bR)-5-Hydroxy-3a-(2-methanesulfonyloxy-ethyl)-4-oxo-6-(toluene-4-sulfonyl)-2,3,3a,4,5,5a,6,11,12,12b-decahydro-1H-6,12a-diaza-indeno[7,1-cd]fluorene-5-carboxylic acid methyl ester
  参考文献：
  名称：

  A dipolar cycloaddition approach toward the kopsifoline alkaloid framework

  摘要：

  Using a metal-catalyzed domino reaction as the key step, the heterocyclic skeleton of the kopsifoline alkaloid family was constructed by a 1,3-dipolar cycloaddition of a carbonyl ylide dipole derived from a Rh(II)-catalyzed reaction of a diazo ketoester across the indole pi-bond. Ring opening of the resulting 1,3-dipolar cycloadduct followed by a reductive dehydroxylation step resulted in the formation of a critical silyl enol ether necessary for the final F-ring closure of the kopsifoline skeleton. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.01.064
• 作为产物：
  描述：

  1-苄氧基-2-碘乙烷 在 4-二甲氨基吡啶 、 氢氧化钾 、 正丁基锂 、 4 A molecular sieve 、 水 、 三乙胺 、 甲烷磺酰基叠氮化物 、 magnesium chloride 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 89.17h， 生成 methyl 3-(3-(2-(benzyloxy)ethyl)-2-oxo-1-(2-(1-tosyl-1H-indol-3-yl)acetyl)-piperidin-3-yl)-2-diazo-3-oxopropanoate
  参考文献：
  名称：

  A dipolar cycloaddition approach toward the kopsifoline alkaloid framework

  摘要：

  Using a metal-catalyzed domino reaction as the key step, the heterocyclic skeleton of the kopsifoline alkaloid family was constructed by a 1,3-dipolar cycloaddition of a carbonyl ylide dipole derived from a Rh(II)-catalyzed reaction of a diazo ketoester across the indole pi-bond. Ring opening of the resulting 1,3-dipolar cycloadduct followed by a reductive dehydroxylation step resulted in the formation of a critical silyl enol ether necessary for the final F-ring closure of the kopsifoline skeleton. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.01.064

文献信息

• Rhodium Carbenoid Induced Cycloadditions of Diazo Ketoimides Across Indolyl π-Bonds
  作者：Albert Padwa、Xuechuan Hong、José Mejía-Oneto、Stefan France

  DOI：10.1055/s-2007-967982

  日期：2007.3

  chloride and alkyl 2-diazo-3-(3-substituted-2-oxopiperidin-3-yl)-3-oxopropanoates were treated with rhodium(II) acetate. Attack of the imido carbonyl oxygen at the resultant rhodium carbenoid center produced a transient push-pull carbonyl ylide dipole which underwent an intramolecular dipolar cycloaddition across the indole π-bond. In most cases, the resulting cycloadduct is the consequence of ENDO-cycloaddition

  一系列由 (1 H-indol-3-yl) 乙酰氯和烷基 2-重氮-3-(3-取代-2-氧代哌啶-3-基)-3-氧代丙酸酯制备的重氮酮酰亚胺用铑(II)处理) 醋酸盐。亚氨基羰基氧在所得铑卡宾中心的攻击产生了瞬态推拉羰基叶立德偶极子，该偶极子在吲哚π-键上经历了分子内偶极环加成。在大多数情况下，产生的环加合物是关于偶极子的 ENDO 环加成的结果，这完全符合最低能量过渡态。有趣的是，当乙酸叔丁酯取代基位于起始重氮酮亚胺的环连接处时，EXO-环加合物是获得的唯一产物。在这种情况下，
• Cycloaddition Protocol for the Assembly of the Hexacyclic Framework Associated with the Kopsifoline Alkaloids
  作者：Xuechuan Hong、Stefan France、José M. Mejía-Oneto、Albert Padwa

  DOI：10.1021/ol062029z

  日期：2006.10.1

  An approach to the hexacyclic framework of the kopsifoline alkaloids has been developed and is based on a Rh(II)-catalyzed cyclization-cycloaddition cascade. The resulting [3+2]-cycloadduct was readily converted into the TBS enol ether 23. Oxidation of the primary alcohol present in 23 followed by reaction with CsF afforded compound 24 that contains the complete hexacyclic skeleton of the kopsifolines.
• A dipolar cycloaddition approach toward the kopsifoline alkaloid framework
  作者：Xuechuan Hong、Stefan France、Albert Padwa

  DOI：10.1016/j.tet.2007.01.064

  日期：2007.6

  Using a metal-catalyzed domino reaction as the key step, the heterocyclic skeleton of the kopsifoline alkaloid family was constructed by a 1,3-dipolar cycloaddition of a carbonyl ylide dipole derived from a Rh(II)-catalyzed reaction of a diazo ketoester across the indole pi-bond. Ring opening of the resulting 1,3-dipolar cycloadduct followed by a reductive dehydroxylation step resulted in the formation of a critical silyl enol ether necessary for the final F-ring closure of the kopsifoline skeleton. (C) 2007 Elsevier Ltd. All rights reserved.