triphenylsilyl triflate | 27607-76-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: triphenylsilyl triflate
• 英文别名: Ph₃SiOTf；Triphenyl(trifluoromethylsulfonyloxy)silane；triphenylsilyl trifluoromethanesulfonate
• CAS: 27607-76-7
• 化学式: C₁₉H₁₅F₃O₃SSi
• 分子量: 408.473
• InChiKey: ZQTHWOBTFAQXKR-UHFFFAOYSA-N

物化性质

• 沸点：
  413.1±45.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.52
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  triphenylsilyl triflate 在 dirhodium tetraacetate 、 N,N-二异丙基乙胺 、 methyloxirane 作用下， 以 乙醚 、 甲苯 为溶剂， 生成 benzyl 2-triphenylsilyl-2-oxoacetate
  参考文献：
  名称：

  Synthesis and Use of α-Silyl-Substituted α-Hydroxyacetic Acids

  摘要：

  Rhodium-catalyzed oxygen transfer was used to generate benzyl 2-sifyi-2-oxoacetates in good yields. The hydrogenation of these compounds led to chiral alpha-silyl-substituted a-hydroxyacetic acids. Resolution by means of HPLC using a chiral stationary phase afforded an enantiomerically pure representative of this class of compounds, which was successfully applied as a chiral ligand in an asymmetric aldol-type reaction.

  DOI：

  10.1021/ol025911n
• 作为产物：
  描述：

  三氟甲磺酸 、 烯丙基三苯基硅烷 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 triphenylsilyl triflate
  参考文献：
  名称：

  Improved Preparation of N-Trimethylsilylpyridinium Triflate, N-Triphenylsilylpyridinium Triflate, N-Triisopropylsilylpyridinium Triflate and Their Use in Silylating Alcohols to Silyl Ethers

  摘要：

  N-硅基吡啶季盐三氟甲磺酸盐1a-c以优异的产率通过相应的烯丙基硅烷与三氟甲磺酸反应后加入吡啶制备得到。化合物1a-c被用于从醇中通常以高产率制备硅基醚。开发了一种便捷的程序，使得在产物分离中无需水洗即可实现醇的硅烷化。

  DOI：

  10.1055/s-1997-1421

文献信息

• Activation of Carbon Dioxide by Silyl Triflate-Based Frustrated Lewis Pairs
  作者：Sarah A. Weicker、Douglas W. Stephan

  DOI：10.1002/chem.201501904

  日期：2015.9.7

  Silyl triflates of the form R4−nSi(OTf)n (n=1, 2; OTf=OSO3CF3) are shown to activate carbon dioxide when paired with bulky alkyl‐substituted Group 15 bases. Combinations of silyl triflates and 2,2,6,6‐tetramethylpiperidine react with CO2 to afford silyl carbamates via a frustrated Lewis pair‐type mechanism. With trialkylphosphines, the silyl triflates R3Si(OTf) reversibly bind CO2 affording [R′3P(CO2)SiR3][OTf]

  R 4- n Si（OTf）n（n = 1，2; OTf = OSO 3 CF 3）形式的甲硅烷基三氟甲磺酸酯与庞大的烷基取代的15组碱配对时，可以活化二氧化碳。甲硅烷基三氟甲磺酸酯和2,2,6,6-四甲基哌啶的混合物与CO 2反应，通过沮丧的Lewis对机制，生成氨基甲酸酯硅烷基酯。与三烷基膦，甲硅烷基三氟甲磺酸酯[R 3的Si（OTF）可逆地结合CO 2得到[R' 3 P（CO 2）的SIR 3 ] [光学传递函数]，而当PH 2的Si（OTF）2是使用一种或CO的两个分子2可以隔离。后者的bis-CO 2产品在低温下和过量的磷化氢很受青睐。
• Is the phosphaethynolate anion, (OCP)−, an ambident nucleophile? A spectroscopic and computational study
  作者：Dominikus Heift、Zoltán Benkő、Hansjörg Grützmacher

  DOI：10.1039/c3dt53569j

  日期：——

  The reactivity of Na(OCP) was investigated towards triorganyl compounds of the heavier group 14 elements (R3EX R = Ph or iPr; E = Si, Ge, Sn, Pb; X = Cl, OTf). In the case of E = Si two constitutional isomers were formed and characterised in situ: R3Si–O–CP is the kinetic and R3Si–PCO is the thermodynamic product, representing experimental evidence of the ambident character of the (OCP)− anion. Applying theoretical calculations and spectroscopic methods, the compound previously reported as iPr3Si–O–CP can now unambiguously be identified as iPr3Si–PCO. The heavier analogues form exclusively the phosphaketene isomer R3E–PCO (E = Ge, Sn, Pb). DFT calculations were performed to gain deeper insight into the bonding and thermodynamic stability of these compounds.

  对Na(OCP)与较重第14族元素的三有机化合物(R3EX R = Ph或iPr; E = Si, Ge, Sn, Pb; X = Cl, OTf)的反应性进行了研究。在E = Si的情况下,形成了两种构造异构体并进行了原位表征:R3Si-O-CP是动力学产物,R3Si-PCO是热力学产物,代表了(OCP)⁻阴离子的双位特性的实验证据。应用理论计算和光谱方法,先前报道的化合物iPr3Si-O-CP现在可以明确地被鉴定为iPr3Si-PCO。较重的类似物仅形成磷卡烯异构体R3E-PCO(E = Ge, Sn, Pb)。进行了DFT计算,以深入了解这些化合物的键合和热力学稳定性。
• Direct synthesis of 4,4-disubstituted N-silyl-1,4-dihydropyridines
  作者：Jan Bräckow、Klaus T. Wanner

  DOI：10.1016/j.tet.2005.11.069

  日期：2006.3

  based on the trapping reaction of 4-substitued N-silylpyridinium ions. When performed with dialkylmagnesium reagents, such as iPr2Mg, silyl protected 4,4-disubstituted 1,4-dihydropyridines were obtained in up to quantitative yields. High 1,4-selectivity was found for sterically demanding nucleophiles, whereas small nucleophiles (Me2Mg) tend to yield 1,2-addition-products. Grignard, dialkylzinc and organocopper

  提出了制备4，4-二取代的1，4-二氢吡啶的空前的方法。它基于4-取代的N-甲硅烷基吡啶鎓离子的捕集反应。当与二烷基镁试剂，如执行我镨2的Mg，甲硅烷基保护4,4-二取代的高达定量的产率得到1,4-二氢吡啶。发现对空间要求高的亲核试剂具有较高的1,4-选择性，而小的亲核试剂（Me 2 Mg）倾向于产生1,2-加成产物。发现格氏试剂，二烷基锌和有机铜试剂没有产生加成产物或产生较差的结果。在HCl存在下，用NaCNBH 3还原获得的1,4-二氢吡啶，然后用二碳酸叔丁酯以高收率提供了相应的N- Boc保护的哌啶。
• Catalytic Enantioselective Quick Route to Aldol-Tethered 1,6- and 1,7-Enynes from ω-Unsaturated Aldehydes
  作者：Jesús M. García、José M. Odriozola、Jesús Razkin、Irati Lapuerta、Amaiur Odriozola、Iñaki Urruzuno、Silvia Vera、Mikel Oiarbide、Claudio Palomo

  DOI：10.1002/chem.201404452

  日期：2014.11.17

  developed based on a direct cross‐aldol reaction between ω‐unsaturated aldehydes and propargylic aldehydes (α,β‐ynals) promoted by combined α,α‐dialkylprolinol ether/Brønsted acid catalysis. This synergistic activation strategy is key to accessing the corresponding aldol adducts with high stereoselectivity, both enantio‐ and diastereoselectivity. The aldol reaction also proceeds well with propargylic ketones

  基于结合α​​，α-二烷基脯氨醇促进的ω-不饱和醛与炔醛（α，β-醛基）之间的直接交叉羟醛反应，已开发出一种有效的不对称官能化1,6-和1,7-炔烃的路线。醚/布朗斯台德酸催化。这种协同活化策略是获得对映体和非对映体选择性高的立体选择性高的相应羟醛加合物的关键。醛醇缩合反应还可与炔丙基酮（α，β-炔酮）进行得很好，从而可以立体控制途径获得相应的叔醇。这些加合物的实用性很难通过标准方法进行制备，通过使用标准Pauson-Khand条件将其转化为三取代双环烯酮得以证明。
• Generation of chiral N-acylpyridinium ions by means of silyl triflates and their diastereoselective trapping reactions: formation of N-acyldihydropyridines and N-acyldihydropyridones
  作者：Cornelia E Hoesl、Markus Maurus、Jörg Pabel、Kurt Polborn、Klaus Th Wanner

  DOI：10.1016/s0040-4020(02)00675-0

  日期：2002.8

  An efficient method for the generation of chiral N-acylpyridinium salts from various pyridines and a chiral acid chloride promoted by means of silyl triflates as additives is presented. The stereoselective addition of organometallic reagents to the intermediate chiral N-acylpyridinium ions led to α-substituted N-acyldihydropyridines and N-acyldihydropyridones in good yields, whereas no or minor amounts

  提出了一种由各种吡啶和通过甲硅烷基三氟甲磺酸酯作为添加剂促进的手性酰氯生成手性N-酰基吡啶鎓盐的有效方法。将有机金属试剂立体选择性地添加到中间体手性N-酰基吡啶二鎓离子中，可以以良好的收率得到α-取代的N-酰基二氢吡啶和N-酰基二氢吡啶酮，而当采用标准方法不使用甲硅烷基三氟甲磺酸酯作为添加剂时，则没有或仅有少量的产物。根据使用哪种吡啶或有机金属试剂，观察到良好的非对映选择性。在碱性或还原反应条件下，手性助剂的去除均能顺利进行。