1,2-bis(2,2-diphenyl-1,3-dioxolan-4-yl)ethane-1,2-diol | 898568-52-0

• 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: 1,2-bis(2,2-diphenyl-1,3-dioxolan-4-yl)ethane-1,2-diol
• 英文别名: 1,2:5,6-di-O-diphenylmethylidene-D-mannitol；(1S,2S)-1,2-bis((R)-2,2-diphenyl-1,3-dioxolan-4-yl)ethane-1,2-diol；(1S,2S)-1,2-bis[(4R)-2,2-diphenyl-1,3-dioxolan-4-yl]ethane-1,2-diol
• CAS: 898568-52-0
• 化学式: C₃₂H₃₀O₆
• 分子量: 510.587
• InChiKey: JYYZLBSVMGEBAY-SKKKGAJSSA-N

物化性质

• 沸点：
  684.9±50.0 °C(Predicted)
• 密度：
  1.276±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  38
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,2-bis(2,2-diphenyl-1,3-dioxolan-4-yl)ethane-1,2-diol 在 lead(IV) acetate 、 三乙胺 作用下， 以 乙酸乙酯 、 甲苯 、 苯 为溶剂， 反应 32.17h， 生成 (S)-1-Benzyl-2-((S)-2,2-diphenyl-[1,3]dioxolan-4-yl)-2,7-dihydro-1H-furo[3,4-b]pyridin-5-one
  参考文献：
  名称：

  Torquoselective 6π-Electron Electrocyclic Ring Closure of 1-Azatrienes Containing Acyclic Chirality at the C-Terminus

  摘要：

  Torquoselective pericyclic ring closures of 1-azatrienes that contain acyclic chirality at the C-terminus are described herein.

  DOI：

  10.1021/ol060932t
• 作为产物：
  描述：

  甘露醇 、 苯甲酮二甲基缩酮 在 tin(ll) chloride 作用下， 以 乙二醇二甲醚 为溶剂， 反应 16.0h， 生成 1,2-bis(2,2-diphenyl-1,3-dioxolan-4-yl)ethane-1,2-diol
  参考文献：
  名称：

  催化束缚策略：简单的醛催化分子间烯烃氢胺化

  摘要：

  在本文中，我们描述了一种催化束缚策略，其中简单的醛预催化剂通过临时分子内、室温分子间加氢胺化反应和邻二胺的合成来实现。该催化剂允许由烯丙胺和羟胺形成混合胺醛，从而导致容易的分子内加氢胺化事件。用手性醛获得的有希望的对映选择性也突出了这种催化束缚方法在不对称催化中的潜力，并证明仅依赖临时分子内的有效对映诱导是可能的。

  DOI：

  10.1021/ja208867g

文献信息

• Synthesis of<scp>d</scp>-mannitol-based crown ethers and their application as catalyst in asymmetric phase transfer reactions
  作者：Tamás Nemcsok、Zsolt Rapi、György Keglevich、Alajos Grün、Péter Bakó

  DOI：10.1002/chir.22800

  日期：2018.4

  A few new d‐mannitol‐based monoaza‐15‐crown‐5 type chiral lariat ethers and 18‐crown‐6 type macrocycles were synthesized. These crown compounds were used as phase transfer catalysts in asymmetric Michael addititons and in a Darzens condensation under mild conditions to afford the corresponding products in a few cases in good to excellent enantioselectivities. In the Michael addition of diethyl acetoxymalonate

  一些新的d基于-mannitol-单氮杂15-冠-5型手性套索醚和18-冠-6型大环合成。这些冠状化合物在温和条件下在不对称迈克尔加成反应中和在Darzens缩合反应中用作相转移催化剂，在少数情况下可提供具有良好至优异对映选择性的相应产物。在将乙酰氧基丙二酸二乙酯迈克尔加成反查尔酮，在将乙酰氨基丙二酸二乙酯添加至ß-硝基苯乙烯中，在溴代丙二酸二乙酯与亚苄基丙二腈的反应中，在溴代丙二酸二乙酯与2-亚苄基-1,3-茚满二酮的环丙烷化反应中，并且在α的Darzens凝聚中与苯甲醛-chloroacetophenone，39％，65％，99％，56％，和62％的最大的对映选择性，分别在存在下得到d -mannitol基于大环化合物作为催化剂。
• Chiral Amino Diol Derivatives as New Modular Organocatalysts for the Enantioselective α-Chlorination of Cyclic β-Keto Esters
  作者：Pablo Etayo、Ramón Badorrey、María D. Díaz-de-Villegas、José A. Gálvez

  DOI：10.1002/adsc.201000594

  日期：2010.12.17

  Highly modular chiral amino diol derivatives have been used as organocatalysts in the enantioselective α-chlorination of cyclic β-keto esters. Optimization of the catalyst structure and the reaction conditions has allowed the synthesis of optically active α-chlorinated products with high enantioselectivities (up to 96% ee) using inexpensive commercially available N-chlorosuccinimide (NCS) as the chlorine

  在环状β-酮酯的对映选择性α-氯化中，高度模块化的手性氨基二醇衍生物已被用作有机催化剂。催化剂结构和反应条件的优化允许使用廉价的市售N-氯代琥珀酰亚胺（NCS）作为氯源，在温和的条件下合成具有高对映选择性（高达96％ee）的旋光性α氯化产物。
• An Expeditious Method for the First Asymmetric Synthesis of Dexoxadrol from the Chiral Pool
  作者：María Díaz-de-Villegas、José Gálvez、Pablo Etayo、Ramón Badorrey、Pilar López-Ram-de-Víu

  DOI：10.1055/s-0030-1258110

  日期：2010.7

  high-yielding methodology for the asymmetric synthesis of 2-(1,3-dioxolan-4-yl)piperidines is described. This approach involves a highly stereoselective addition of vinylmagnesium bromide to N-(3-butenyl)imines derived from D-glyceraldehyde diphenyl ketal and a ring-closing metathesis reaction as key steps. This procedure was used for the first asymmetric synthesis of (S)-2-[(S)-2,2-diphenyl-1,3-di

  描述了一种用于不对称合成 2-(1,3-dioxolan-4-yl) 哌啶的新的、直接且高产的方法。该方法涉及将乙烯基溴化镁高度立体选择性地添加到衍生自 D-甘油醛二苯缩酮的 N-(3-丁烯基) 亚胺中，并将闭环复分解反应作为关键步骤。该程序用于第一次不对称合成 (S)-2-[(S)-2,2-diphenyl-1,3-dioxolan-4-yl]piperidine (dexoxolan-4-yl) 哌啶 (dexoxadrol)，从方便保护的 D-甘露醇开始，在六个以 43% 的总收益率前进。
• Synthesis and SAR studies of chiral non-racemic dexoxadrol analogues as uncompetitive NMDA receptor antagonists
  作者：Ashutosh Banerjee、Dirk Schepmann、Jens Köhler、Ernst-Ulrich Würthwein、Bernhard Wünsch

  DOI：10.1016/j.bmc.2010.09.047

  日期：2010.11.15

  A series of chiral non-racemic dexoxadrol analogues with various substituents in position 4 of the piperidine ring was synthesized and pharmacologically evaluated. Only the enantiomers having (S)-configuration at the 2-position of the piperidine ring and 4-position of the dioxolane ring were considered. Key steps in the synthesis were an imino-Diels-Alder reaction of enantiomerically pure imine (S)-13, which had been obtained from D-mannitol, with Danishefsky's Diene 14 and the replacement of the p-methoxybenzyl protective group with a Cbz-group. It was shown that (S,S)-configuration of the ring junction (position 2 of the piperidine ring and position 4 of the dioxolane ring) and axial orientation of the C-4-substituent ((4S)-configuration) are crucial for high NMDA receptor affinity. 2-(2,2-Diphenyl-1,3-dioxolan-4-yl)piperidines with a hydroxy moiety ((S,S,S)-5, K-i = 28 nM), a fluorine atom ((S,S,S)-6, WMS-2539, K-i = 7 nM) and two fluorine atoms ((S,S)-7, K-i = 48 nM) in position 4 represent the most potent NMDA antagonists with high selectivity against sigma(1) and sigma(2) receptors and the polyamine binding site of the NMDA receptor. The NMDA receptor affinities of the new ligands were correlated with their electrostatic potentials, calculated gas phase proton affinities (negative enthalpies of deprotonation) and dipole moments. According to these calculations decreasing proton affinity and increasing dipole moment are correlated with decreasing NMDA receptor affinity. (C) 2010 Elsevier Ltd. All rights reserved.