2-[2'-(5,5-dimethyl-1,3,2-dioxaphosphorinano)]-2,3-didehydrothiolane 1-oxide | 849148-29-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: 2-[2'-(5,5-dimethyl-1,3,2-dioxaphosphorinano)]-2,3-didehydrothiolane 1-oxide
• 英文别名: 5,5-dimethyl-1,3,2-dioxaphosphorinanyl-2,3-didehydro-thiolane 1-oxide；5,5-Dimethyl-2-(1-oxo-2,3-dihydrothiophen-5-yl)-1,3,2lambda5-dioxaphosphinane 2-oxide；5,5-dimethyl-2-(1-oxo-2,3-dihydrothiophen-5-yl)-1,3,2λ5-dioxaphosphinane 2-oxide
• CAS: 849148-29-4
• 化学式: C₉H₁₅O₄PS
• 分子量: 250.255
• InChiKey: QZLVQELZBJVYJW-UHFFFAOYSA-N

物化性质

• 熔点：
  116 °C
• 沸点：
  430.6±45.0 °C(Predicted)
• 密度：
  1.36±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  71.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  叔丁基硫醇 、 2-[2'-(5,5-dimethyl-1,3,2-dioxaphosphorinano)]-2,3-didehydrothiolane 1-oxide 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以74%的产率得到3-tert-butylsulfanyl-2-[2'-(5,5-dimethyl-1,3,2-dioxaphosphorinanyl)]thiolane 1-oxide
  参考文献：
  名称：

  Diastereoselective Michael additions to α,β-unsaturated α-sulfinyl phosphonates in the thiolane series

  摘要：

  A chiral racemic 2-phosphono-2,3-didehydrothiolane sulfoxide was used as a Michael acceptor in the reactions with several nucleophiles, in particular thiols. In most cases the reactions were fully diastereoselective. The relative configuration of the resulting adducts was determined. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.11.098
• 作为产物：
  描述：

  2-[2'-(5,5-dimethyl-1,3,2-dioxaphosphorinano)]thiolane 1-oxide 在 sodium periodate 、 三氟乙酸酐 作用下， 以 乙醚 、 乙醇 、 水 为溶剂， 反应 3.0h， 生成 2-[2'-(5,5-dimethyl-1,3,2-dioxaphosphorinano)]-2,3-didehydrothiolane 1-oxide
  参考文献：
  名称：

  硫烷系列中α-亚磺酰基膦酸酯的不对称合成

  摘要：

  通过非对映选择性S-氧化和使用手性恶唑烷的动力学拆分，获得了一系列对映体富集的2-膦酰硫杂环戊烷亚砜。用相同的氧化剂对相应的2-膦酰基-2,3-二氢呋喃酮进行对映选择性氧化，得到相应的亚砜，其ee最高可达98％。

  DOI：

  10.1016/j.tetasy.2004.11.019

文献信息

• Investigations on enzyme catalytic promiscuity: The first attempts at a hydrolytic enzyme-promoted conjugate addition of nucleophiles to α,β-unsaturated sulfinyl acceptors
  作者：Lidia Madalińska、Małgorzata Kwiatkowska、Tomasz Cierpiał、Piotr Kiełbasiński

  DOI：10.1016/j.molcatb.2012.05.002

  日期：2012.9

  Looking for new examples of enzyme catalytic promiscuity, attempts were made to use hydrolytic enzymes as catalysts for a conjugate addition of nucleophiles toα,β-unsaturated sulfinyl derivatives. The addition of piperidine to phenyl vinyl sulfoxide in chloroform proceeded both in the enzyme-catalyzed and non-catalyzed process, while in the former case the reaction was 2.5-fold faster. On the contrary

  寻找酶催化混杂的新实例，尝试使用水解酶作为亲核试剂向α，β-不饱和亚磺酰基衍生物的共轭加成的催化剂。在氯仿中，在酶催化和非催化过程中都将哌啶加到苯基乙烯基亚砜中，而在前一种情况下，反应快2.5倍。相反，仅在酶存在下并且使用乙醇作为溶剂时，才将苯硫醇与苯基乙烯基亚砜的共轭加成反应。在任何情况下都没有对映体富集产物。但是，将苯硫醇添加到更好的Michael受体上，即环状α-亚磺酰基烯基膦酸酯，在某些情况下，在各种脂肪酶的存在下，在动力学拆分条件下进行的操作给出的产物和回收的底物均具有高达25％的光学纯度。尽管立体选择性和这些反应的速率很低，但这是脂肪酶催化迈克尔将杂原子亲核试剂加成到α，β-不饱和杂有机受体上的第一个例子。提出了一些机械方面的考虑。
• Michael addition to a chiral non-racemic 2-phosphono-2,3-didehydrothiolane S-oxide
  作者：Mihaela Gulea、Małgorzata Kwiatkowska、Piotr Łyżwa、Remi Legay、Annie-Claude Gaumont、Piotr Kiełbasiński

  DOI：10.1016/j.tetasy.2008.12.034

  日期：2009.2

  The Michael addition of selected sulfur and nitrogen nucleophiles to a chiral non-racemic 2-phosphono2,3-didehydrothiolane S-oxide is fully diastereoselective. The enantiomeric excesses of the adducts obtained could be determined by P-31 NMR spectroscopy using (R)-(+)-tert-butyl(phenyl)phosphinothioic acid as a chiral solvating agent. The addition of thiophenol was monitored by P-31 NMR spectroscopy which made it possible to observe the formation and evolution of the kinetic and thermodynamic adducts in the reaction mixture. The structures of both enantiomeric thiophenol adducts have been determined by X-ray analysis. (C) 2009 Elsevier Ltd. All rights reserved.
• Diastereoselective Michael additions to α,β-unsaturated α-sulfinyl phosphonates in the thiolane series
  作者：Piotr Łyżwa、Aleksandra Jankowiak、Małgorzata Kwiatkowska、Marian Mikołajczyk、Piotr Kiełbasiński、Alexander Betz、Paul-Alain Jaffres、Annie-Claude Gaumont、Mihaela Gulea

  DOI：10.1016/j.tetlet.2006.11.098

  日期：2007.1

  A chiral racemic 2-phosphono-2,3-didehydrothiolane sulfoxide was used as a Michael acceptor in the reactions with several nucleophiles, in particular thiols. In most cases the reactions were fully diastereoselective. The relative configuration of the resulting adducts was determined. (c) 2006 Elsevier Ltd. All rights reserved.
• Asymmetric synthesis of α-sulfinylphosphonates in the thiolane series
  作者：Piotr Kielbasinski、Piotr Lyzwa、Marian Mikolajczyk、Mihaela Gulea、Margareth Lemarié、Serge Masson

  DOI：10.1016/j.tetasy.2004.11.019

  日期：2005.2

  A series of enantiomerically enriched 2-phosphonothiolane sulfoxides were obtained by diastereoselective S-oxidation combined with kinetic resolution using a chiral oxaziridine. Enantioselective oxidation of the corresponding 2-phosphono-2,3-didehydrothiolanes with the same oxidizing agent led to the corresponding sulfoxides with ee up to 98%.

  通过非对映选择性S-氧化和使用手性恶唑烷的动力学拆分，获得了一系列对映体富集的2-膦酰硫杂环戊烷亚砜。用相同的氧化剂对相应的2-膦酰基-2,3-二氢呋喃酮进行对映选择性氧化，得到相应的亚砜，其ee最高可达98％。