2-(trimethylsilyl)-2-cyclopentenyl hydroperoxide | 156518-14-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 2-(trimethylsilyl)-2-cyclopentenyl hydroperoxide
• 英文别名: (5-Hydroperoxycyclopenten-1-yl)-trimethylsilane
• CAS: 156518-14-8
• 化学式: C₈H₁₆O₂Si
• 分子量: 172.299
• InChiKey: PEHHWCJOMUCQBT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.44
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)-2-cyclopentenyl hydroperoxide 生成 (S)-2-Trimethylsilanyl-cyclopent-2-enyl-hydroperoxide
  参考文献：
  名称：

  Biocatalytic kinetic resolution of hydroperoxy vinylsilanes by horseradish peroxidase (HRP) and lipases, a comparative study

  摘要：

  The kinetic resolution of hydroperoxy vinylsilanes 1 has been investigated by the horseradish-peroxidase(HRP)-catalyzed reduction with guaiacol and by the acetylation with isopropenyl acetate in the presence of various lipases. The best results (ee values up to 89% at 48% conversion) were obtained for the lipase-catalyzed reactions. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00197-3
• 作为产物：
  描述：

  环戊烯-1-基(三甲基)硅烷 以72%的产率得到
  参考文献：
  名称：

  Adam Waldemar, Richter Markus J., J. Org. Chem., 59 (1994) N 12, S 3335- 3340

  摘要：

  DOI：

文献信息

• Asymmetric Synthesis with the Enzyme <i>Coprinus</i> Peroxidase:  Kinetic Resolution of Chiral Hydroperoxides and Enantioselective Sulfoxidation
  作者：Waldemar Adam、Cordula Mock-Knoblauch、Chantu R. Saha-Möller

  DOI：10.1021/jo990201p

  日期：1999.6.1

  hydroperoxide 1a afforded with CiP enantiomerically enriched hydroperoxide 1a (ee up to 54%) and alcohol 2a (ee up to 40%), as well as ketone 3a (which is also formed simultaneously in all other reactions) and molecular oxygen. Catalase activity was established for CiP with hydrogen peroxide. When aryl alkyl sulfides 4 were used as oxygen acceptors, three products, sulfoxides 5, alcohols 2, and hydroperoxides

  Coprinus过氧化物酶（CiP）用于外消旋氢过氧化物1的动力学拆分和前手性硫化物4的不对称硫氧化。在动力学分辨率的条件下，CiP和愈创木酚作为还原剂还原了11种氢过氧化物1a-k，对映选择性最高> （S）-氢过氧化物1的98％和（R）-醇2的90％。在没有还原剂的情况下，氢过氧化物1a提供了CiP对映异构体富集的氢过氧化物1a（ee最高为54％）和醇2a（ ee高达40％），酮3a（在所有其他反应中也同时形成）和分子氧。用过氧化氢确定了CiP的过氧化氢酶活性。将芳基烷基硫化物4用作氧受体时，得到三种产物：亚砜5，醇2和氢过氧化物1，全部以对映体富集的形式存在。衍生自萘基甲基硫化物（4f）的亚砜的最高ee值（89％）。因此，CiP可用于光学活性氢过氧化物1，醇2和亚砜5的不对称合成。
• Regioselectivity of the Singlet Oxygen Ene Reaction (Schenck Reaction) with Vinylsilanes
  作者：Waldemar Adam、Markus J. Richter

  DOI：10.1021/jo00091a020

  日期：1994.6

  The ene reaction-of singlet oxygen and vinylsilanes 1 with various substitution patterns and double-bond geometry has been studied. beta-Silyl allylic hydroperoxides 2 were the major products of the photooxygenation, accompanied by smaller amounts of alpha,beta-unsaturated ketones 3. The latter derive from decomposition of the regioisomeric alpha-hydroperoxy silanes 4 by elimination of silanol. Regioselectivities up to 97:3 were observed for vinylsilanes with a methyl group geminal to the silyl group and with cyclic derivatives. Z-Configurated substrates showed lower regioselectivity and reactivity. Elongation of the carbon chain at the geminal position also increased the amount enone formed. These results are rationalized in terms of stereoelectronic effects imposed by the silyl group on the ring-opening of the perepoxide intermediate.