Methyldiphenyl(trifluormethylsulfonyloxy)silan | 91158-37-1

• 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: Methyldiphenyl(trifluormethylsulfonyloxy)silan
• 英文别名: diphenylmethylsilyl trifluoromethanesulfonate；methyldiphenylsilyl trifluoromethanesulfonate；methyldiphenylsilyl triflate；Ph2MeSiOTf；Methyl(diphenyl)silyl trifluoromethanesulfonate；[methyl(diphenyl)silyl] trifluoromethanesulfonate
• CAS: 91158-37-1
• 化学式: C₁₄H₁₃F₃O₃SSi
• 分子量: 346.402
• InChiKey: RMMZVIVQUFAVLE-UHFFFAOYSA-N

物化性质

• 沸点：
  334.3±42.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.24
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  Methyldiphenyl(trifluormethylsulfonyloxy)silan 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-methyl(diphenyl)silyl-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：

  Diphenyl(trifluormethansulfonyloxymethyl)silan 以 neat (no solvent) 为溶剂， 生成 Methyldiphenyl(trifluormethylsulfonyloxy)silan
  参考文献：
  名称：

  Tacke, Reinhold; Wiesenberger, Frank; Becker, Beate, Chemische Berichte, 1992, vol. 125, # 3, p. 591 - 606

  摘要：

  DOI：

文献信息

• Organocatalytic Enantioselective α-Hydroxymethylation of Aldehydes: Mechanistic Aspects and Optimization
  作者：Robert K. Boeckman、Kyle F. Biegasiewicz、Douglas J. Tusch、John R. Miller

  DOI：10.1021/acs.joc.5b00380

  日期：2015.4.17

  Further studies of the direct enantioselective α-hydroxymethylation of aldehydes employing the α,α-diarylprolinol trimethylsilyl ether class of organocatalysts are described. This process has proven efficient for access to β-hydroxycarboxylic acids and δ-hydroxy-α,β-unsaturated esters from aldehydes in generally good yields, excellent enantioselectivity, and compatibility with a broad range of functional

  描述了使用α，α-二芳基脯氨醇三甲基甲硅烷基醚类有机催化剂对醛类的直接对映选择性α-羟甲基化的进一步研究。已证明该方法有效地以通常良好的收率，优异的对映选择性以及与醛中广泛的官能团的相容性从醛获得β-羟基羧酸和δ-羟基-α，β-不饱和酯。这些研究的目的是确定影响α-羟甲基化过程的收率和对映选择性的关键反应变量，例如催化剂的结构，介质的pH值，反应物和试剂的纯度，特别是关于酸性杂质的存在，缓冲液的性质以及标准变量，包括溶剂，时间，温度和混合效率。先前鉴定的中间体乳醇已被进一步表征，并对其反应性进行了检测。这些研究已导致鉴定最关键的变量，这些变量直接转化为改善的底物范围，可再现性，对映选择性和产率。
• Terminal Iron Carbyne Complexes Derived from Arrested CO ₂ Reductive Disproportionation
  作者：Charles C. Mokhtarzadeh、Curtis E. Moore、Arnold L. Rheingold、Joshua S. Figueroa

  DOI：10.1002/anie.201705877

  日期：2017.8.28

  reacts with two molecules of CO2 to effect reductive disproportionation to CO and carbonate ([CO3]2−). When the reaction is performed in the presence of silyl triflates, reductive disproportionation is arrested by silylative esterification of a mono-CO2 adduct. This results in the formation of four-coordinate terminal iron carbynes possessing an aryl carbamate substituent owing to the direct attachment

  阻碍的四异氰化物二价阴离子Na 2 [Fe（CNAr ）4 ]与两个CO 2分子反应，导致还原歧化为CO和碳酸盐（[CO 3 ] 2-）。当反应在甲硅烷基三氟甲磺酸酯存在下进行时，还原性歧化被单-CO 2加合物的甲硅烷基化酯化所阻止。由于C（O）OSiR 3的直接连接，导致具有芳基氨基甲酸酯取代基的四配位末端铁卡宾的形成基团形成异氰酸酯氮原子。这些铁碳多重键合物种的晶体学，光谱学和计算分析表明，其电子结构性质表明构象锁定的铁碳炔单元。
• Three-Component Coupling Reactions of Silylglyoxylates, Alkynes, and Aldehydes:  A Chemoselective One-Step Glycolate Aldol Construction
  作者：David A. Nicewicz、Jeffrey S. Johnson

  DOI：10.1021/ja043884l

  日期：2005.5.1

  A single-pot three-component coupling reaction of silylglyoxylates (1), terminal alkynes, and aldehydes in the presence of ZnI2 and Et3N is presented. The products of the reaction, densely functionalized silyl-protected glycolate aldols (2), can be converted to the corresponding acetonides (3) in a one-pot deprotection/ketalization sequence. A variety of terminal alkynes and aldehydes can be successfully employed to give a range of highly functionalized, fully protected 1,2-diols in good yields and moderate diastereoselectivities. Mechanistic experiments suggest that the zinc acetylide reacts with the silylgyloxylate (1) in a chemoselective manner. Using an unoptimized (+)-N-methylephedrine and Zn(OTf)2 system, silyl-deprotected adduct 2 was formed in 64% ee and 89:11 dr.
• The first example of nickel-catalyzed silyl-Heck reactions: direct activation of silyl triflates without iodide additives
  作者：Jesse R. McAtee、Sara E.S. Martin、Andrew P. Cinderella、William B. Reid、Keywan A. Johnson、Donald A. Watson

  DOI：10.1016/j.tet.2014.03.021

  日期：2014.7

  For the first time, nickel-catalyzed silyl-Heck reactions are reported. Using simple phosphine-supported nickel catalysts, direct activation of silyl triflates has been achieved. These results contrast earlier palladium-catalyzed systems, which require iodide additives to activate silyl-triflates. These nickel-based catalysts exhibit good functional group tolerance in the preparation of vinyl silanes, and unlike earlier systems, allows for the incorporation of trialkylsilanes larger than Me₃Si.
• <i>Ortho</i>-Silylated Derivatives of Tetrakis(2-hydroxyphenyl)ethene: A Sterically Isolated Structural Model for Oxo-Surface Binding Domains
  作者：Mee-Kyung Chung、Owen C. Lightbody、Jeffrey M. Stryker

  DOI：10.1021/ol801427w

  日期：2008.9.1

  The introduction of sterically isolating ortho-trialkylsilyl, -aryldialkylsilyl, and -diarylalkylsilyl substituents onto the structurally preorganized tetrakis(2-hydroxyphenyl)ethene ligand framework has been accomplished by a 4-fold retro-Brook rearrangement. Installation of the most sterically demanding silyl substituents required the development of an iterative procedure, involving successive double silylation/metalation/migration sequences without the isolation of intermediates. This system was designed to function as a soluble structural model for the planar binding domains of heterogeneous "oxo-surfaces" of silica and alumina supports.