[difluoro(phenylseleno)methyl]trimethylsilane | 868761-01-7

• 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: [difluoro(phenylseleno)methyl]trimethylsilane
• 英文别名: PhSeCF2TMS；[Difluoro(phenylselanyl)methyl]-trimethylsilane
• CAS: 868761-01-7
• 化学式: C₁₀H₁₄F₂SeSi
• 分子量: 279.263
• InChiKey: KOWXABGSSCWOHZ-UHFFFAOYSA-N

物化性质

• 沸点：
  241.7±40.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.49
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [difluoro(phenylseleno)methyl]trimethylsilane 、 2-萘甲醛 在 copper diacetate 、 1,2-双(二苯基膦)乙烷 、 盐酸 作用下， 以 N,N-二甲基甲酰胺 、 四氢呋喃 为溶剂， 反应 21.0h， 以94%的产率得到2,2-difluoro-1-(naphthalen-2-yl)-2-(phenylselanyl)ethanol
  参考文献：
  名称：

  Lewis acid-catalyzed tri- and difluoromethylation reactions of aldehydes

  摘要：

  首次报道了在TiF4/DMF、Ti(OiPr)4/DMF和Cu(OAc)2/dppp/甲苯条件下，三甲基硅基三氟甲基（Me3SiCF3）与醛的Lewis酸催化三氟甲基化反应。我们还成功地应用这种方法，使用Me3SiCF2SePh、Me3SiCF2P(O)OEt2和Me3SiCF2SPh实现了醛的双氟甲基化。

  DOI：

  10.1039/b603041f
• 作为产物：
  描述：

  苯硒酚 在 sodium tetrahydroborate 、 sodium hydride 、 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 0.83h， 生成 [difluoro(phenylseleno)methyl]trimethylsilane
  参考文献：
  名称：

  Synthesis and Transformation of [Difluoro(phenylseleno)methyl]- trimethylsilane

  摘要：

  [GRAPHIC]A novel and efficient strategy was developed to synthesize [difluoro(phenylseleno)methyl]trimethylsilane (PhSeCF2-TMS, 2), which was further utilized as a nucleophilic difluoromethylating reagent to incorporate the difluoro(phenylseleno)methyl (PhSeCF2) group into carbonyl compounds in good yields. The resulting PhSeCF2-containing alcohols 3 could be conveniently converted into corresponding difluoromethyl alcohols 4 by a radical deselenylation.

  DOI：

  10.1021/jo051119z

文献信息

• Synthesis of difluorinated carbocyclic analogues of 5-deoxypentofuranoses
  作者：Gaëlle Fourrière、Jérôme Lalot、Nathalie Van Hijfte、Jean-Charles Quirion、Eric Leclerc

  DOI：10.1016/j.tetlet.2009.09.170

  日期：2009.12

  The synthesis of difluorinated carbocyclic analogues of 5-deoxypentofuranoses is described. The sequence involves an addition of PhSeCF2TMS to carbohydrate-derived aldehydes followed by a radical cyclization, and provides a secure strategy for a future synthesis of pentofuranoses and nucleoside analogues.

  描述了5-脱氧戊呋喃糖酶的二氟化碳环类似物的合成。该序列涉及将PhSeCF 2 TMS添加到碳水化合物衍生的醛中，然后进行自由基环化，并为将来合成戊呋喃糖酶和核苷类似物提供了安全的策略。
• Remote asymmetric trifluoromethylation induced by chiral sulfinyl group: synthesis of enantiomerically pure 1-(2-naphthyl)-2,2,2-trifluoroethanol
  作者：Hideki Sugimoto、Shuichi Nakamura、Yoshihiro Shibata、Norio Shibata、Takeshi Toru

  DOI：10.1016/j.tetlet.2005.12.061

  日期：2006.2

  The reaction of 1-[(2,4,6-triisopropylphenyl)sulfinyl]-2-naphthaldehyde with (trifluoromethyl)trimethylsilane using tetramethylammonium fluoride gave trifluoromethylated compounds in high yield with high diastereoselectivity. Desilylation and subsequent recrystallization yielded the enantiomerically and diastereomerically pure trifluoroethanol, which afforded chiral 1-(2-naphthyl)-2,2,2-trifluoroethanol

  使用四甲基氟化铵使1-[（（2,4,6-三异丙基苯基）亚磺酰基] -2-萘醛与（三氟甲基）三甲基硅烷反应，以高收率和高非对映选择性得到三氟甲基化化合物。脱甲硅烷基化和随后的重结晶得到对映异构体和非对映异构体纯的三氟乙醇，在除去亚磺酰基后得到手性的1-（2-萘基）-2,2,2-三氟乙醇。
• Synthesis of difluorinated carbocyclic analogues of 5-deoxypentofuranoses and 1-amino-5-deoxypentofuranoses: en route to fluorinated carbanucleosides
  作者：Gaëlle Fourrière、Nathalie Van Hijfte、Jérôme Lalot、Guy Dutech、Bruno Fragnet、Gaël Coadou、Jean-Charles Quirion、Eric Leclerc

  DOI：10.1016/j.tet.2010.03.079

  日期：2010.5

  The synthesis of difluorinated carbocyclic analogues of 5-deoxypentofuranoses and 1-amino-5-deoxypentofuranoses is described. The sequence involves an addition of PhSeCF2TMS to carbohydrate-derived aldehydes or their corresponding tert-butanesulfinylimines followed by a radical cyclization. Optimized conditions for the PhSeCF2TMS addition to alpha-chiral aldehydes have been disclosed and its unusual diastereoselectivity is discussed. Application of the sequence using Ellman's auxiliary allows a more direct access to 1-aminopentose analogues with a complete control of the pseudo-anomeric center configuration. (C) 2010 Elsevier Ltd. All rights reserved.
• Synthesis of exo-methylenedifluorocyclopentanes as precursors of fluorinated carbasugars by 5-exo-dig radical cyclization
  作者：Gaëlle Fourrière、Eric Leclerc、Jean-Charles Quirion、Xavier Pannecoucke

  DOI：10.1016/j.jfluchem.2011.02.015

  日期：2012.2

  The synthesis of polyhydroxylated 1,1-difluoro-5-methylenecyclopentanes is described. The sequence involves an addition of PhSeCF2TMS to a tartrate-derived aldehyde or its corresponding tert-butanesulfinylimines followed by a radical cyclization. The use of a benzyl protected substrate led to an unproductive 1,5-hydrogen transfer after cyclization but the desired compound was eventually obtained from the unprotected substrate. A hydroboration/oxidation sequence was investigated on these 1,1-difluoro-5-methylenecyclopentanes as it would provide fluorinated carbasugars, a new and promising class of glycomimetics. Unfortunately, this reaction was poorly efficient and its regioselectivity not the expected one. (C) 2011 Elsevier B.V. All rights reserved.
• Synthesis and Transformation of [Difluoro(phenylseleno)methyl]- trimethylsilane
  作者：Ying-Ying Qin、Xiao-Long Qiu、Yan-Yan Yang、Wei-Dong Meng、Feng-Ling Qing

  DOI：10.1021/jo051119z

  日期：2005.10.1

  [GRAPHIC]A novel and efficient strategy was developed to synthesize [difluoro(phenylseleno)methyl]trimethylsilane (PhSeCF2-TMS, 2), which was further utilized as a nucleophilic difluoromethylating reagent to incorporate the difluoro(phenylseleno)methyl (PhSeCF2) group into carbonyl compounds in good yields. The resulting PhSeCF2-containing alcohols 3 could be conveniently converted into corresponding difluoromethyl alcohols 4 by a radical deselenylation.