3-(1S-hydroxy-2-(p-toluenesulfonyl)oxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine | 142169-24-2

• 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: 3-(1S-hydroxy-2-(p-toluenesulfonyl)oxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine
• 英文别名: [(2S)-2-(1,5-dihydro-2,4-benzodioxepin-3-yl)-2-hydroxyethyl] 4-methylbenzenesulfonate
• CAS: 142169-24-2
• 化学式: C₁₈H₂₀O₆S
• 分子量: 364.419
• InChiKey: IDQCPVBMZZIWAL-KRWDZBQOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  90.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-(1S-hydroxy-2-(p-toluenesulfonyl)oxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine 在 sodium methylate 作用下， 以 甲醇 、 水 为溶剂， 反应 1.0h， 生成 (S)-(-)-3-(1,2-epoxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine
  参考文献：
  名称：

  Asymmetric dihydroxylation of acrolein acetals: synthesis of stable equivalents of Enantiopure glyceraldehyde and glycidaldehyde

  摘要：

  Asymmetric dihydroxylation (ADH) of acrolein acetals afforded optically active glyceraldehyde equivalents. Enantiopure 3-(1,2-dihydroxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine 3, a protected glyceraldehyde, was obtained from the corresponding acrolein acetal 2 by ADH and subsequent recrystallization. Enantiopure 3-(1,2-epoxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine 5, a protected glycidaldehyde, was produced in two steps from 3.

  DOI：

  10.1016/0040-4039(92)88149-y
• 作为产物：
  描述：

  邻苯二甲醇 在 吡啶 、 potassium dioxotetrahydroxoosmate(VI) 、 dihydroquinidine 0-O-(9'-phenanthryl) ether 、 potassium carbonate 、 对甲苯磺酸 、 potassium hexacyanoferrate(III) 、 原甲酸三甲酯 作用下， 以 水 、 叔丁醇 为溶剂， 反应 48.0h， 生成 3-(1S-hydroxy-2-(p-toluenesulfonyl)oxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine
  参考文献：
  名称：

  Asymmetric dihydroxylation of acrolein acetals: synthesis of stable equivalents of Enantiopure glyceraldehyde and glycidaldehyde

  摘要：

  Asymmetric dihydroxylation (ADH) of acrolein acetals afforded optically active glyceraldehyde equivalents. Enantiopure 3-(1,2-dihydroxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine 3, a protected glyceraldehyde, was obtained from the corresponding acrolein acetal 2 by ADH and subsequent recrystallization. Enantiopure 3-(1,2-epoxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine 5, a protected glycidaldehyde, was produced in two steps from 3.

  DOI：

  10.1016/0040-4039(92)88149-y

文献信息

• Transformations of the tetracyclic skeleton of eudistomins by neighboring-group participation in the Mitsunobu reaction
  作者：Jan H. van Maarseveen、Elna H. H. Oberyé、Marjon B. Bolster、Hans W. Scheeren、Chris G. Kruse

  DOI：10.1002/recl.19951140107

  日期：——

  tetracyclic ring system, now with a 1,5,2-oxathiazine ring. Substitution of the hydroxyl group in a trans 1-hydroxy dethia carba eudistomin derivative (i.e. with a 1,2-oxazepine ring) also gave rearranged products due to transannular interaction from the bridgehead nitrogen atom, to give via an aziridinium ion intermediate, products with a 6,5,7,6-membered tetracyclic ring system containing an 1,2-oxazine

  Mitsunobu反应介导将氮亲核试剂引入反式1-羟基eudistomins中，从而获得高收率的重排产物，而不是由于邻近基团的参与而导致的预期的cis eudistomins。在1,6,2-oxathiazepine环中的硫原子在6,5,6,7元四环系统中进行环过相互作用，生成含硫th离子的中间体，随后本亲核分子的分子间攻击得到一个6,5,6,6元四环系统，现在带有1,5,2-恶二嗪环。在所涉及的羟基的取代反式1-羟基去硫卡巴eudistomin衍生物（即 （具有1,2-氧杂氮杂环的化合物）也由于桥头氮原子的跨环相互作用而产生了重排产物，并通过叠氮鎓离子中间体提供了具有6,5,7,6-元四环体系的产物，其中1， 2-恶嗪环。
• Optically active enantiomers of substituted glyceraldehydes or
  申请人：Massachusetts Institute of Technology

  公开号：US05162554A1

  公开（公告）日：1992-11-10

  Stable, optically active enantiomers of substituted glyceraldehydes or glycidaldehydes are synthesized by using osmium-catalyzed asymmetric dihydroxylation of an olefin which is a substituted 1,5-dihydro-3H-2,4-benzodioxepine. For example, the protected glyceraldehyde, 3-(1,2-dihydroxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine and the protected glycidaldehyde, 3-(1,2-epoxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine have been synthesized and the optical enantiomer has been recovered. In the synthetic and isolation methods, enantiomers with high enantiomeric excess are recovered from the mother liquor following a recrystallization step.

  使用奥斯米姆催化不对称二羟基化合成了取代甘油醛或甘氧醛的稳定、光学活性对映体，该催化反应的底物是取代的1,5-二氢-3H-2,4-苯并二氧杂环戊烯。例如，合成了保护的甘油醛，3-(1,2-二羟乙基)-1,5-二氢-3H-2,4-苯并二氧杂环戊烯和保护的甘氧醛，3-(1,2-环氧乙基)-1,5-二氢-3H-2,4-苯并二氧杂环戊烯，并回收了光学对映体。在合成和分离方法中，通过重新结晶步骤从母液中回收高对映体过量的对映体。
• US5162554A
  申请人：——

  公开号：US5162554A

  公开（公告）日：1992-11-10
• [EN] SUBSTITUTED 1,5-DIHYDRO-3H-2,4-BENZODIOXEPINES AS OPTICALLY ACTIVE GLYDERALDEHYDES OR GLYCIDALDEHYDES
  申请人：MASSACHUSETTS INSTITUTE OF TECHNOLOGY

  公开号：WO1992022546A1

  公开（公告）日：1992-12-23

  (EN) Stable, optically active enantiomers of substituted glyceraldehydes or glycidaldehydes are synthesized by using osmium-catalyzed asymmetric dihydroxylation of an olefin which is a substituted 1,5-dihydro-3H-2,4-benzodioxepine. For example, the protected glyceraldehyde. 3-(1,2-dihydroxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine and the protected glycidaldehyde, 3-(1,2-epoxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine have been synthesized and the optical enantiomer has been recovered. In the synthetic and isolation methods, enantiomers with high enantiomeric excess are recovered from the mother liquor following a recrystallization step.(FR) Enantiomères stables, optiquement actifs, de glycéraldéhydes ou de glycidaldéhydes substitués synthétisés par dihydroxylation asymétrique à catalyse d'osmium d'une oléfine constituée par une 1,5-dihydro-3H-2,4-benzodioxépine substituée. Par exemple, le glycéraldéhyde protégé, 3-(1,2-dihydroxyéthyl)-1,5-dihydro-3H-2,4-benzodioxépine et le glycidaldéhyde protégé, 3-(1,2-époxyéthyl)-1,5-dihydro-3H-2,4-benzodioxépine ayant été synthétisés et l'énantiomère optique a été récupéré. Selon les méthodes de synthèse et d'isolation, les énantiomères à exédent énantiomérique élevé sont récupérés à partir de la liqueur mère après l'étape de recristallisation.
• Asymmetric dihydroxylation of acrolein acetals: synthesis of stable equivalents of Enantiopure glyceraldehyde and glycidaldehyde
  作者：Ryu Oi、K.Barry Sharpless

  DOI：10.1016/0040-4039(92)88149-y

  日期：1992.4

  Asymmetric dihydroxylation (ADH) of acrolein acetals afforded optically active glyceraldehyde equivalents. Enantiopure 3-(1,2-dihydroxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine 3, a protected glyceraldehyde, was obtained from the corresponding acrolein acetal 2 by ADH and subsequent recrystallization. Enantiopure 3-(1,2-epoxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine 5, a protected glycidaldehyde, was produced in two steps from 3.