(1,1-difluoroprop-1-en-2-yloxy)trimethylsilane | 1018435-02-3

• 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: (1,1-difluoroprop-1-en-2-yloxy)trimethylsilane
• 英文别名: 1,1-difluoro-2-trimethylsilyoxypropene；1,1-Difluoro-2-(trimethylsilyloxy)-1-propene；1,1-difluoroprop-1-en-2-yloxy(trimethyl)silane
• CAS: 1018435-02-3
• 化学式: C₆H₁₂F₂OSi
• 分子量: 166.243
• InChiKey: BHXCTOMZLJXNDB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.97
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-乙酰氧基-2,3,5-三苯甲酰氧基-1-beta-D-呋喃核糖 、 (1,1-difluoroprop-1-en-2-yloxy)trimethylsilane 在 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以66%的产率得到3,5-Di-O-benzoyl-1,2-O-(2,2-difluoro-3-oxo-1-phenylbut-1-ylidene)-α-D-ribofuranose
  参考文献：
  名称：

  二氟烯氧基硅烷与糖基供体的反应：二氟-C-糖苷和二氟-C-二糖的合成。

  摘要：

  由酰基硅烷和三氟甲基三甲基硅烷在氟化物活化下制得的二氟烯氧基硅烷与某些糖基供体（酰基糖苷，糖基）进行糖基化反应，制得具有二氟亚甲基基团的异氟-C-糖苷代替异头氧。该反应强烈取决于糖基供体2-位的取代基。该方法在木糖衍生的酰基硅烷上的应用导致形成了二氟-C-二糖，是一种等排的O-糖基模拟物。

  DOI：

  10.1002/1521-3765(20010216)7:4<903::aid-chem903>3.0.co;2-m
• 作为产物：
  描述：

  三甲基氯硅烷 、 1,1-difluoro-1-(phenylsulfonyl)propan-2-one 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以70%的产率得到(1,1-difluoroprop-1-en-2-yloxy)trimethylsilane
  参考文献：
  名称：

  Synthesis of Fluorinated β-Ketosulfones and gem-Disulfones by Nucleophilic Fluoroalkylation of Esters and Sulfinates with Di- and Monofluoromethyl Sulfones

  摘要：

  An efficient and practically useful method for the preparation of alpha-functionalized mono- and difluoro(phenylsulfonyl)methanes by using a nucleophilic fluoroalkylation methodology was developed. alpha,alpha-Difluoro-P-ketosulfones, alpha-monofluoro-beta-ketosulfones, and alpha-fluoro disulfones were successfully prepared in excellent yields by nucleophilic fluoroalkylation of esters and sulfinates with PhSO2CF2H and PhSO2CH2F reagents.

  DOI：

  10.1021/jo900320b

文献信息

• Mixed Organofluorine−Organosilicon Chemistry. 13. One-Pot Synthesis of Difluoroaldols from Acylsilanes and Trifluoromethyltrimethylsilane. Application to the Synthesis of a Difluoro Analogue of Egomaketone
  作者：Olivier Lefebvre、Thierry Brigaud、Charles Portella

  DOI：10.1021/jo001549j

  日期：2001.3.1

  3 were synthesized in a one-pot procedure involving an acylsilane 1, trifluoromethyltrimethylsilane (TFMTMS), and an aldehyde. The key intermediate of this reaction is a difluoroenoxysilane 2. Ytterbium triflate proved to be a very efficient catalyst for promoting the aldol type reaction under very mild conditions. The potential of this reaction for the convergent synthesis of difluorinated compounds

  通过一锅法合成二氟醛醇化合物3，该方法涉及酰基硅烷1，三氟甲基三甲基硅烷（TFMTMS）和醛。该反应的关键中间体是二氟乙氧基硅烷2。三氟甲磺酸Y被证明是在非常温和的条件下促进醛醇型反应的非常有效的催化剂。通过相应的醛醇化合物3d的脱水合成二氟庚基酮7d，说明了该反应对二氟化合物的收敛合成的潜力。
• Acetyltrimethylsilane, Trifluoromethyltrimethylsilane, and Prenyl Esters:  A Three-Component System for the Synthesis of <i>g</i><i>em</i>-Difluoroanalogues of Monoterpenes
  作者：Olivier Lefebvre、Thierry Brigaud、Charles Portella

  DOI：10.1021/jo010245+

  日期：2001.6.1

  Optimized conditions leading to either the desired enol silyl ether or the unprecedented methyl(trifluoromethyl)trimethylsilyl carbinol 4 have been achieved. The prenylation of the enol silyl ether gives a 9/1 mixture of regioisomers, in favor of the expected ketone 1. Treatment of 1 with vinylmagnesium bromide leads to (+/-)-4,4-difluorolinalool 7. Reaction with the lithium enolate of ethyl diethylphosphonoacetate

  描述了3,3-二氟-6-甲基庚-5-烯-2-酮1的制备，这是合成4,4-二氟萜烯的关键中间体，及其在芳樟醇和香叶醇系列中的应用。该方法涉及1，1-二氟-2-三甲基甲硅烷氧基丙烯，由乙酰基三甲基硅烷和三氟甲基三甲基硅烷制备的烯醇甲硅烷基醚，并在三甲基甲硅烷基三氟甲磺酸酯的催化下，与异戊烯基苯甲酸酯原位反应。已经获得了导致所需的烯醇甲硅烷基醚或空前的甲基（三氟甲基）三甲基甲硅烷基甲醇4的最佳条件。烯醇甲硅烷基醚的异戊烯酸酯化形成区域异构体的9/1混合物，有利于预期的酮1。用乙烯基溴化镁处理1得到（+/-）-4,4-二氟芳樟醇7。
• Convergent synthesis of fluoro and gem-difluoro compounds using trifluoromethyltrimethylsilane
  作者：Charles Portella、Thierry Brigaud、Olivier Lefebvre、Richard Plantier-Royon

  DOI：10.1016/s0022-1139(99)00158-x

  日期：2000.2

  Trifluorotrimethylsilane reacts with acylsilanes to give the corresponding difluoroenoxysilanes via the Brook rearrangement of the alcoholate adducts. The difluoroenoxysilane reacts in situ with various types of electrophilic substrates, leading to gem-difluoro functionalized derivatives in a one-pot methodology. This paper describes reactions with Michael accepters, prenyl, benzyl and glycosyl donors leading to 2,2-difluoro-1,5-diketones, 4,4- or 6,6-difluorocyclohexenones, o- or p-fluorophenols, difluoro analogues of terpenes, and difluoro-C-glycosides. (C) 2000 Elsevier Science S.A. All rights reserved.
• Umpolung Reactivity of Difluoroenol Silyl Ethers with Amines and Amino Alcohols. Application to the Synthesis of Enantiopure α-Difluoromethyl Amines and Amino Acids
  作者：Florent Huguenot、Anne Billac、Thierry Brigaud、Charles Portella

  DOI：10.1021/jo702328v

  日期：2008.4.1

  Difluoroenol silyl ethers, produced in situ from acylsilanes and CF3TMS, react as electrophiles with amines to give difluoroimines, via the corresponding hemiaminal adduct, as evidenced by F-19 NMR spectroscopy. Reaction with (R)-phenylglycinol led to 2-difluoromethyloxazolidines. After separation of the diastereomers, reduction with LAH and Strecker-type synthesis gave enantiopure alpha-difluoromethy-lamines and alpha-difluoromethyl-alpha-amino acids, respectively.
• Synthesis of Fluorinated β-Ketosulfones and <i>gem</i>-Disulfones by Nucleophilic Fluoroalkylation of Esters and Sulfinates with Di- and Monofluoromethyl Sulfones
  作者：Chuanfa Ni、Laijun Zhang、Jinbo Hu

  DOI：10.1021/jo900320b

  日期：2009.5.15

  An efficient and practically useful method for the preparation of alpha-functionalized mono- and difluoro(phenylsulfonyl)methanes by using a nucleophilic fluoroalkylation methodology was developed. alpha,alpha-Difluoro-P-ketosulfones, alpha-monofluoro-beta-ketosulfones, and alpha-fluoro disulfones were successfully prepared in excellent yields by nucleophilic fluoroalkylation of esters and sulfinates with PhSO2CF2H and PhSO2CH2F reagents.