1,4,9,12-tetraoxa-dispiro[4.2.4.2]tetradecane-2,3,10,11-tetracarboxylic acid tetramethyl ester

• 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: 1,4,9,12-tetraoxa-dispiro[4.2.4.2]tetradecane-2,3,10,11-tetracarboxylic acid tetramethyl ester
• 英文别名: tetramethyl (2R,3R,10R,11R)-1,4,9,12-tetraoxadispiro[4.2.48.25]tetradecane-2,3,10,11-tetracarboxylate
• 化学式: C₁₈H₂₄O₁₂
• 分子量: 432.381
• InChiKey: PWZMANVIENAACU-DDHJBXDOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  142
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  1,4,9,12-tetraoxa-dispiro[4.2.4.2]tetradecane-2,3,10,11-tetracarboxylic acid tetramethyl ester 、 magnesium,1H-pyren-1-ide,bromide 以 四氢呋喃 为溶剂， 反应 24.0h， 以21%的产率得到(R,R,R,R)-⁽²⁾-trans,trans-2,3,10,11-tetrakis(hydroxydipyren-1-ylmethyl)-1,4,9,12-tetraoxadispiro[4.2.4.2]tetradecane
  参考文献：
  名称：

  手性布朗斯台德酸介导的对映选择性光环加成反应：Rocaglamides 的不对称合成

  摘要：

  罗卡格酸甲酯和相关天然产物罗卡格莱胺和罗卡格洛尔的对映选择性合成概述。该方法涉及由手性布朗斯台德酸 (TADDOL) 促进的对映选择性 [3 + 2] 光环加成反应，以提供 aglain 前体，然后是酮醇转移/还原序列到 rocaglate 核心。

  DOI：

  10.1021/ja062621j
• 作为产物：
  描述：

  L-(+)-酒石酸二甲酯 、 1,4-环己二酮 在 三氟化硼乙醚 作用下， 以 乙酸乙酯 为溶剂， 反应 7.0h， 以64%的产率得到1,4,9,12-tetraoxa-dispiro[4.2.4.2]tetradecane-2,3,10,11-tetracarboxylic acid tetramethyl ester
  参考文献：
  名称：

  手性布朗斯台德酸介导的对映选择性光环加成反应：Rocaglamides 的不对称合成

  摘要：

  罗卡格酸甲酯和相关天然产物罗卡格莱胺和罗卡格洛尔的对映选择性合成概述。该方法涉及由手性布朗斯台德酸 (TADDOL) 促进的对映选择性 [3 + 2] 光环加成反应，以提供 aglain 前体，然后是酮醇转移/还原序列到 rocaglate 核心。

  DOI：

  10.1021/ja062621j

文献信息

• Asymmetric Synthesis of Rocaglamides via Enantioselective Photocycloaddition Mediated by Chiral Bronsted Acids
  申请人：Porco, JR. John A.

  公开号：US20090299081A1

  公开（公告）日：2009-12-03

  The present invention provides a new strategies for the synthesis of compounds of the rocaglamide family and related natural products. The synthetic approach generally involves photochemical generation of an oxidopyrylium species from a 3-hydroxychromone derivative followed by an enantioselective 1,3-dipolar cycloaddition of the oxidopyrylium species to a dipolarophile in the presence of a TADDOL derivative. This approach can be used for the formation of adducts containing an aglain core structure. Methods of the conversion of aglain core structures to aglain, rocaglamide and forbaglin ring systems are also provided. The present invention also relates to the use of rocaglamide/aglain/forbaglin derivatives for the manufacture of medicaments for use in the treatment of cancer or cancerous conditions, disorders associated with cellular hyperproliferation, or NF-κB-dependent conditions.
• ASYMMETRIC SYNTHESIS OF ROCAGLAMIDES VIA ENANTIOSELECTIVE PHOTOCYCLOADDITION MEDIATED BY CHIRAL BRONSTED ACIDS
  申请人：Porco, JR. John A.

  公开号：US20120238766A1

  公开（公告）日：2012-09-20

  The present invention provides a new strategies for the synthesis of compounds of the rocaglamide family and related natural products. The synthetic approach generally involves photochemical generation of an oxidopyrylium species from a 3-hydroxychromone derivative followed by an enantioselective 1,3-dipolar cycloaddition of the oxidopyrylium species to a dipolarophile in the presence of a TADDOL derivative. This approach can be used for the formation of adducts containing an aglain core structure. Methods of the conversion of aglain core structures to aglain, rocaglamide and forbaglin ring systems are also provided. The present invention also relates to the use of rocaglamide/aglain/forbaglin derivatives for the manufacture of medicaments for use in the treatment of cancer or cancerous conditions, disorders associated with cellular hyperproliferation, or NF-κB-dependent conditions.
• US8137509B2
  申请人：——

  公开号：US8137509B2

  公开（公告）日：2012-03-20
• US8404088B2
  申请人：——

  公开号：US8404088B2

  公开（公告）日：2013-03-26
• [EN] ASYMMETRIC SYNTHESIS OF ROCAGLAMIDES VIA ENANTIOSELECTIVE PHOTOCYCLOADDITION MEDIATED BY CHIRAL BRONSTED ACIDS<br/>[FR] SYNTHÈSE ASYMÉTRIQUE DE ROCAGLAMIDES PAR PHOTOCYCLOADDITION ÉNENTIOSÉLECTIVE INDUITE PAR DES ACIDES DE BRÖNSTED CHIRAUX
  申请人：UNIV BOSTON

  公开号：WO2007139749A2

  公开（公告）日：2007-12-06

  [EN] The present invention provides a new strategies for the synthesis of compounds of the rocaglamide family and related natural products. The synthetic approach generally involves photochemical generation of an oxidopyrylium species from a 3-hydroxychromone derivative followed by an enantioselective 1,3-dipolar cycloaddition of the oxidopyrylium species to a dipolarophile in the presence of a TADDOL derivative. This approach can be used for the formation of adducts containing an aglain core structure. Methods of the conversion of aglain core structures to aglain, rocaglamide and forbaglin ring systems are also provided. The present invention also relates to the use of rocaglamide/aglain/forbaglin derivatives for the manufacture of medicaments for use in the treatment of cancer or cancerous conditions, disorders associated with cellular hyperproliferation, or NF-?B-dependent conditions.
  [FR] La présente invention concerne de nouvelles stratégies pour la synthèse de composés de la famille des rocaglamides et de produits naturels apparentés. Le procédé comporte la production photochimique d'une espèce d'oxydopyrylium à partir d'un dérivé de 3-hydroxychromone, suivie d'une oxydation cyclique 1,3-dipolaire énantiosélective de l'espèce d'oxydopyrylium en dipolarophile en présence d'un dérivé de TADDOL. Cette approche peut être utilisée pour la formation de produits d'addition contenant une structure centrale aglaïne. L'invention concerne également des procédés permettant de transformer les structures centrales aglaïne en systèmes de noyau aglaïne, rocaglamide et forbagline. La présente invention concerne également l'utilisation de dérivés de rocaglamide/aglaïne/forbagline pour la fabrication de médicaments destinés à être utilisés dans le traitement du cancer ou de pathologies cancéreuses, de troubles associés à l'hyperprolifération cellulaire ou d'états NF-?B-dépendants.