triphenylsilyl formate | 18670-64-9

• 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: triphenylsilyl formate
• 英文别名: Triphenyl-formoxy-silan；formic acid triphenylsilanyl ester；Ameisensaeure-triphenylsilylester；Formyloxy-triphenyl-silan
• CAS: 18670-64-9
• 化学式: C₁₉H₁₆O₂Si
• 分子量: 304.42
• InChiKey: HMJSMIIPSSPJMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.83
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  三苯基氯硅烷 、 alkaline earth salt of/the/ methylsulfuric acid 生成 triphenylsilyl formate
  参考文献：
  名称：

  Thermal Rearrangements of Organosilicon and Organogermanium Compounds¹

  摘要：

  DOI：

  10.1021/ja01623a042

文献信息

• Synthesis of silyl formates, formamides, and aldehydes <i>via</i> solvent-free organocatalytic hydrosilylation of CO₂
  作者：Takumi Murata、Mahoko Hiyoshi、Manussada Ratanasak、Jun-ya Hasegawa、Tadashi Ema

  DOI：10.1039/d0cc01371d

  日期：——

  formates, formamides, and aldehydes. Tetrabutylammonium acetate (TBAA) catalyzed the solvent-free N-formylation of amines with CO2 and hydrosilane to give formamides including Weinreb formamide, Me(MeO)NCHO, which was successively converted into aldehydes by one-pot reactions with Grignard reagents.

  二氧化碳（CO2）被用作C1来源以制备甲硅烷基甲酸酯，甲酰胺和醛。乙酸四丁铵（TBAA）催化胺与 和氢硅烷的无溶剂N-甲酰化反应，制得包括Weinreb甲酰胺Me（MeO）NCHO在内的甲酰胺，后者通过与Grignard试剂的一锅反应连续转化为醛。
• A Fluxional Cu ₈ H ₆ Cluster Supported by Bis(diphenylphosphino)methane and its Facile Reaction with CO ₂
  作者：Kanako Nakamae、Miho Tanaka、Bunsho Kure、Takayuki Nakajima、Yasuyuki Ura、Tomoaki Tanase

  DOI：10.1002/chem.201702071

  日期：2017.7.18

  [Cu8(μ-H)6(μ-dppm)5](PF6)2 (dppm=bis(diphenylphosphino)methane) was prepared from reaction of [CuH(PPh3)]6 with dppm in the presence of [Cu(CH3CN)4]PF6 and exhibited fluxional behaviors in solution where the hydrides and the phosphines are scrambling around the trans-bicapped octahedral Cu8 framework. The Cu8H6 complex showed facile reactivity with CO2 (1 atm, RT) to afford a tricopper complex, [Cu

  氢化铜簇[Cu 8（μ-H）6（μ-DPPM）5 ]（PF 6）2（DPPM =双（二苯基膦基）甲烷）是由[CuH（PPh 3）] 6与DPPM在存在[铜（CH的3 CN）4 ] PF 6和在溶液表现出fluxional行为，其中氢化物和膦被加扰围绕反-bicapped八面体的Cu 8框架。Cu 8 H 6络合物与CO 2（1 atm，RT）表现出容易的反应性，从而得到三铜络合物[Cu 3（μ-H）（μ-O 2 CH）（μ-DPPM）3 ] PF 6，它可以被开发以前所未有的CO氢化硅烷化2温和的条件下通过多核CUH物种催化。
• Carbon Dioxide Reduction to Methanol Catalyzed by Mn(I) PNP Pincer Complexes under Mild Reaction Conditions
  作者：Federica Bertini、Mathias Glatz、Berthold Stöger、Maurizio Peruzzini、Luis F. Veiros、Karl Kirchner、Luca Gonsalvi

  DOI：10.1021/acscatal.8b04106

  日期：2019.1.4

  Well-defined Mn(I) hydrido carbonyl PNP pincer-type complexes were tested as efficient and selective nonprecious transition metal catalysts for the reduction of CO2 to MeOH in the presence of hydrosilanes. The choice of reaction temperature and type of silanes proved to be pivotal to achieve fast reactions and high selectivity to the methoxysilyl- vs silylformate derivatives in DMSO. The catalytic

  明确定义的Mn（I）氢化羰基PNP钳型配合物已作为有效和选择性的非贵金属过渡金属催化剂进行了测试，可以在存在氢硅烷的情况下将CO 2还原为MeOH。事实证明，选择反应温度和硅烷类型对于实现快速反应和对DMSO中甲氧基甲硅烷基-甲硅烷基甲酸酯衍生物的高选择性至关重要。催化数据通过DFT计算得到补充，突出显示了以Mn催化剂为中心的逐步CO 2还原机理，而没有金属与配体的协同作用。
• [AsCCAs]-Coordinated Rhenium Hydrides and Their Reactivities Toward Unsaturated Hydrocarbons, Heterocumulenes, and CO₂
  作者：Lukas Eberle、Franka Kreis、Carolin A. M. Stein、Jean-Marc Mörsdorf、Joachim Ballmann

  DOI：10.1021/acs.inorgchem.3c00769

  日期：2023.6.5

  reaction of 3 with PhC≡CPh, ethylene, and CS2, monohydrides of the general formula [AsCCAs]Re(L)H with L = η2-PhC≡CPh (4), η2-H2C═CH2 (5), and η2-CS2 (6) were formed along with H2. In contrast, insertion products of the type [AsCCAs]Re(X)H2 (7–9) were obtained upon treatment of 3 with CyN═C═NCy, PhN═C═O, and Ph2C═C═O, while CO2 failed to react with 3 under identical reaction conditions. Given that several

  具有中央炔烃和两个侧翼砷供体的 [AsCCAs] 配体被用于合成三氢铼络合物，而相应的磷配体被证明不太适合。详细检查了前三氢化物 [AsCCAs]ReH 3 ( 3 ) 的反应性，这表明可能会根据底物进入两个替代反应通道。在3与PhC≡CPh、乙烯和CS 2反应后，通式为[AsCCAs]Re(L)H的单氢化物，其中L = η 2 -PhC≡CPh ( 4 ), η 2 -H 2 C=CH 2 ( 5 ), 和 η 2 -CS2 ( 6 ) 与H 2一起形成。相反，[AsCCAs]Re(X)H 2 ( 7 –9) 类型的插入产物是在用 CyN=C=NCy、PhN=C=O 和 Ph 2 C=C=O 处理3后获得的，而CO 2在相同的反应条件下不能与3反应。鉴于文献中已经报道了CO 2和羰基氢化铼之间的几个生产性反应，通过分别引入 CO 和t BuNC 辅配体， 3进一步衍生化。这导致反式- [AsCCAs]ReH(CO)
• Catalytic synthesis of silyl formates with 1 atm of CO2 and their utilization for synthesis of formyl compounds and formic acid
  作者：Shintaro Itagaki、Kazuya Yamaguchi、Noritaka Mizuno

  DOI：10.1016/j.molcata.2012.10.014

  日期：2013.1

  In the presence of simple Rh-2(OAc)(4) and K2CO3, the hydrosilylation of CO2 (1 atm) with various hydrosilanes efficiently proceeded to afford the corresponding silyl formates in moderate to high yields (53-90% yields). By using the dimethylphenylsilyl formate produced by the hydrosilylation, formamides, formic acid, and a secondary alcohol (via an aldehyde) could be synthesized by the reaction with various nucleophilic reagents such as amines, aniline, water, and the Grignard reagent. (c) 2012 Elsevier B.V. All rights reserved.