ethyltrimethylsilyl-2,2-difluoroketene acetal | 167308-39-6

• 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: ethyltrimethylsilyl-2,2-difluoroketene acetal
• 英文别名: difluoroketene ethyl trimethylsilyl acetal；Difluoroketene ethyl(trimethylsilyl)acetal；(1-ethoxy-2,2-difluoroethenoxy)-trimethylsilane
• CAS: 167308-39-6
• 化学式: C₇H₁₄F₂O₂Si
• 分子量: 196.269
• InChiKey: RCQZKYGTAGIDLZ-UHFFFAOYSA-N

物化性质

• 沸点：
  107.2±40.0 °C(Predicted)
• 密度：
  0.998±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.94
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  苯甲酰氯 、 ethyltrimethylsilyl-2,2-difluoroketene acetal 在 copper(l) chloride 作用下， 以 various solvent(s) 为溶剂， 反应 0.5h， 生成 2,2-二氟-3-氧代-3-苯丙酸乙酯
  参考文献：
  名称：

  Enantioselective synthesis of 2,2-difluoro-3-hydroxycarboxylates by rhodium-catalyzed hydrogenation

  摘要：

  The highly enantioselective synthesis of 2,2-difluoro-3 -hydroxycarboxylates has been achieved by hydrogenating 2,2-difluoro-3-oxocarboxylates in the presence of chiral rhodium-(amidephosphine-phosphinite) complexes. Ethyl 4,4,4-triffluoroacetoacetate can be successfully transformed into the enantiomerically enriched 4,4,4-trifluoro-3-hydroxybutanoate in the same manner. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)01744-5
• 作为产物：
  描述：

  三甲基氯硅烷 、 二氟溴乙酸乙酯 在 1,2-二溴乙烷 、 锌 作用下， 生成 ethyltrimethylsilyl-2,2-difluoroketene acetal
  参考文献：
  名称：

  手性路易斯酸催化醛向二氟乙烯烯基甲缩醛的不对称醛醇醛加成反应

  摘要：

  在亚化学计量的手性路易斯酸2或3的存在下，醛与二氟乙烯乙基三甲基甲硅烷基乙缩醛的醛醇缩合反应（1）提供相应的具有高对映选择性（高达98％ee的α，α-二氟β-羟基酯4-12））。反应温度对醛的对面选择有很大的影响。路易斯酸2在-78和-30℃下催化苄氧基乙醛的反应，分别得到（+）-和（-）-α，α-二氟β-羟基酯7，其光学收率分别为98％和85％。

  DOI：

  10.1016/s0040-4020(97)00683-2

文献信息

• Synthesis of Diverse γ-Aryl-β-ketoesters via Aryne Intermediates Generated by C–C Bond Cleavage
  作者：Keisuke Uchida、Yasunori Minami、Suguru Yoshida、Takamitsu Hosoya

  DOI：10.1021/acs.orglett.9b03418

  日期：2019.11.15

  γ-aryl-β-ketoesters through γ-aryl-β-ketoester-type arynes triggered by C–C bond cleavage has been developed. The Mukaiyama aldol reaction of 6-(triflyloxy)benzocyclobutenones with ketene silyl acetals and subsequent treatment of resulting 6-(triflyloxy)benzocyclobutenols with a base triggered the efficient generation of γ-aryl-β-ketoester-type arynes, which reacted with various arynophiles to provide

  已经开发了一种通过C–C键断裂引发的γ-芳基-β-酮酸酯型芳烃合成各种γ-芳基-β-酮酸酯的方法。6-（三氟乙氧基）苯并环丁烯酮与乙烯酮甲硅烷基乙缩醛的Mukaiyama羟醛反应和随后用碱处理所得的6-（三氟乙氧基）苯并环丁烯醇引发了γ-芳基-β-酮酸酯型芳烃的有效生成，该芳烃与各种嗜酸粒菌反应提供广泛的γ-芳基-β-酮酸酯。通过ALK抑制剂类似物的合成证明了该方法的合成效用。
• Electroreductive Defluorination of Trifluoromethyl Ketones and Trifluoroacetic Acid Derivatives
  作者：Kenji Uneyama、Go Mizutani、Kazushige Maeda、Tsuyoshi Kato

  DOI：10.1021/jo990571d

  日期：1999.9.1

  Difluoroenol silyl ethers 5 and 6, difluoroketene silyl (O,O-, O,S-, and O,N-) acetals 9 and 21, and 2,2-difluoro-2-trimethylsilylacetates 10 were prepared by electroreductive defluorination of trifluoromethyl ketones and trifluoroacetic acid derivatives in an MeCN-TBAB-chlorotrialkylsilane system using a carbon rod as an anode and a lead plate as a cathode. TBAF- or KF-CuI-promoted alpha-alkylation

  二氟乙烯甲硅烷基醚5和6，二氟乙烯甲硅烷基（O，O-，O，S-和O，N-）乙缩醛9和21和2,2-二氟-2-三甲基甲硅烷基乙酸酯10是通过三氟甲基酮的电还原脱氟制备的MeCN-TBAB-氯三烷基硅烷体系中的三氟乙酸衍生物，其中碳棒为阳极，铅板为阴极。TBAF或KF-CuI促进了用亲电子试剂（如醛，酮，亚胺，酰卤和烷基卤化物）促成的10的α-烷基化反应，从而以良好的收率很好地提供了α-烷基化的α，α-二氟乙酸酯。
• Synthesis and biological evaluation of fluorinated analogues of ripostatin A
  作者：Vladyslav Shenderman、Evgeny V. Prusov

  DOI：10.1039/c8ob02890g

  日期：——

  monocyclic derivatives of 14,14′-difluororipostatin A were prepared using a catalytic Mukaiyama aldol reaction, a ring-closing metathesis reaction and a late stage click reaction as key steps. The biological activity of the produced compounds was assessed in vivo using a panel of pathogenic microorganisms. Moderate antibiotic activity was observed for 11-OMe-ripostatin A and 11-OMe-14,14′-difluororipostatin

  使用催化Mukaiyama羟醛反应，闭环易位反应和后期点击反应作为关键步骤，制备了14,14'-二氟ripostatin A的几种单环衍生物。使用一组病原微生物在体内评估了产生的化合物的生物学活性。对于11-OMe-ripostatin A和11-OMe-14,14'-difluororipostatin A观察到中等的抗生素活性。
• Silicon Reagent with Functionalized Tetrafluoroethylene Fragments: Preparation and Coupling with Aldehydes
  作者：Oleg V. Fedorov、Marina I. Struchkova、Alexander D. Dilman

  DOI：10.1021/acs.joc.6b01739

  日期：2016.10.7

  A new fluorinated silicon reagent bearing a functionalized tetrafluoroethylene fragment was prepared from two CF2 building blocks: ethyl bromodifluoroacetate and (bromodifluoromethyl)trimethylsilane. The key C–C bond-forming step involves a difluorocarbene addition/cyclopropane rearrangement sequence. The silicon reagent was coupled with aldehydes and reactive azomethines in the presence of potassium

  由两个CF 2构件：溴二氟乙酸乙酯和（溴二氟甲基）三甲基硅烷制备了一种带有官能化四氟乙烯片段的新型氟化硅试剂。关键的C–C键形成步骤涉及二氟卡宾加成/环丙烷重排序列。在氟化钾存在下，将硅试剂与醛和反应性甲亚胺偶联。
• Isolation of α,α-difluoroketene silyl acetal and its application to asymmetric aldol reactions
  作者：Katsuhiko Iseki、Yoshichika Kuroki、Daisuke Asada、Yoshiro Kobayashi

  DOI：10.1016/s0040-4039(97)00044-0

  日期：1997.2

  Salt-free alpha,alpha-difluoroketene silyl acetal 1 was prepared in pure form. Aldol reactions of 1 with aldehydes catalyzed by catalytic amounts of chiral Lewis acids 2 and 3 proceeded with excellent enantiomeric excess to give optically active alpha,alpha-difluoro-beta-hydroxy esters 4-11 (up to 98% ee). (C) 1997 Elsevier Science Ltd.