triisopropyl((2-methylallyl)oxy)silane | 152549-44-5

• 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: triisopropyl((2-methylallyl)oxy)silane
• 英文别名: methacryloxytriisopropylsilane；2-Methylprop-2-enoxy-tri(propan-2-yl)silane；2-methylprop-2-enoxy-tri(propan-2-yl)silane
• CAS: 152549-44-5
• 化学式: C₁₃H₂₈OSi
• 分子量: 228.45
• InChiKey: OVMWHVQYRVBHEP-UHFFFAOYSA-N

物化性质

• 沸点：
  243.5±9.0 °C(Predicted)
• 密度：
  0.812±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.75
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  triisopropyl((2-methylallyl)oxy)silane 在 selenium(IV) oxide 作用下， 生成 2-(((triisopropylsilyl)oxy)methyl)prop-2-en-1-ol
  参考文献：
  名称：

  N，N-二甲基氨基苯甲酸酯可实现1,1-二取代烯烃的高度对映选择性Sharpless二羟基化†

  摘要：

  设计方案旨在探索经典Sharpless不对称二羟基化（SAD）中有益的催化剂-基底π-π堆积电子相互作用，从而鉴定出高度可极化的烯丙基N，N-二甲基氨基苯甲酸酯作为诱导高水平对映选择性的非常有效的助剂（在传统上具有挑战性的1,1-二取代脂族烯烃底物类别中，ee最高可达99％ee）。

  DOI：

  10.1039/c4ob00621f
• 作为产物：
  描述：

  三异丙基硅基三氟甲磺酸酯 在 chromium dichloride 、 甲醇 、 Ir[dF(CF₃)ppy]₂(5,5'-dCF₃bpy)PF₆ 、 三乙胺 、 4,4'-二叔丁基-2,2'-二吡啶 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 18.0h， 生成 triisopropyl((2-methylallyl)oxy)silane
  参考文献：
  名称：

  烯烃的逆热力学位置异构化

  摘要：

  描述了一种用于烯烃逆热力学位置异构化的光驱动方法。在这项工作中，通过激发态氧化剂和布朗斯台德碱介导，逐步 PCET 活化更取代且热力学更稳定的烯烃底物，提供烯丙基自由基，该自由基被 Cr(II) 助催化剂捕获，从而提供烯丙基铬(III ） 中间的。原位甲醇对这种烯丙基铬络合物的原型脱金属具有高度的区域选择性，并提供异构化且热力学稳定性较差的烯烃产物。较少取代的烯烃异构体的较高氧化电位使其对激发态氧化剂的进一步氧化呈惰性，使其能够在反应过程中在溶液中积累。适用范围广泛的异丙叉底物，包括烯醇醚、烯酰胺、苯乙烯、1,3-二烯和四取代烷基烯烃。还介绍了原型脱金属步骤的机理研究。

  DOI：

  10.1021/jacs.1c11681

文献信息

• Preparation of Alkylmagnesium Reagents from Alkenes through Hydroboration and Boron-Magnesium Exchange
  作者：Markus A. Reichle、Bernhard Breit

  DOI：10.1002/anie.201201704

  日期：2012.6.4

  Tolerant: Alkylmagnesium reagents can be synthesized from alkenes through a sequence of hydroboration and subsequent boron–magnesium exchange using a method that tolerates different functional groups (see scheme). The resulting alkylmagnesium reagents can be used in carbon–carbon bond forming reactions, such as alkylation reactions or transition‐metal‐catalyzed cross‐coupling reactions.

  宽容：烷基镁试剂可从烯烃通过硼氢化反应和随后的硼镁交换的序列使用容忍不同的官能团的方法（参见方案）来合成。所得的烷基镁试剂可用于碳-碳键形成反应，例如烷基化反应或过渡金属催化的交叉偶联反应。
• Synthesis of Dienyl Ketones via Palladium(II)-Catalyzed Direct Cross-Coupling Reactions between Simple Alkenes and Vinyl Ketones: Application to the Synthesis of Vitamin A1 and Bornelone
  作者：Xiang Zhang、Min Wang、Ming-Xin Zhang、Yun-He Xu、Teck-Peng Loh

  DOI：10.1021/ol402692t

  日期：2013.11

  An efficient and general method for the synthesis of conjugated dienyl ketones via palladium(II) acetate catalyzed direct cross-coupling between simple alkenes and vinyl ketones is reported. This method has been successfully applied for the synthesis of Vitamin A1 and bornelone.

  报道了通过乙酸钯（II）催化的简单烯烃与乙烯基酮之间的直接交叉偶联来合成共轭二烯基酮的有效且通用的方法。该方法已成功应用于维生素A1和冰片的合成。
• Alcohol synthesis based on the S_N2 reactions of alkyl halides with the squarate dianion
  作者：Kazuto Sato、Tomoyuki Fujita、Takashi Takeuchi、Takahiro Suzuki、Kazutada Ikeuchi、Keiji Tanino

  DOI：10.1039/d3ob01507f

  日期：——

  A convenient method has been developed for transforming alkyl halides into the corresponding alcohols via an SN2 reaction. Treatment of an alkyl halide with the squarate dianion at high temperature produces mono-alkyl squarate, and a one-pot basic hydrolysis of the intermediate affords the alcohol in good yield.

  已经开发出一种通过S N 2 反应将卤代烷转化为相应醇的简便方法。在高温下用方酸二阴离子处理烷基卤化物产生方酸单烷基酯，中间体的一锅碱性水解以良好的产率提供醇。
• Cr-catalyzed allylic C(sp3)–H addition to aldehydes enabled by photoinduced ligand-to-metal charge transfer
  作者：Xianrong Zeng、Feng-Hua Zhang、Runchen Lai、Xiaoyu Lin、Zhaobin Wang

  DOI：10.1007/s11426-023-1911-x

  日期：2024.5

  chromium (Cr) complexes as catalysts through visible-light-induced LMCT. By investigating the reaction pathway through various mechanistic studies, including radical trapping, kinetic isotope effect (KIE) analysis, and transient absorption spectroscopy, valuable insights have been gained. The proposed mechanism suggests the intermediacy of bromine radicals through homolysis of the Cr–Br bond. Notably

  光诱导配体到金属电荷转移（LMCT）已成为以可持续方式合成有机分子的有效策略。然而，现有的大多数关于通过光诱导LMCT选择性C(sp 3 )–H键功能化的报道都集中在使用后过渡金属或稀土金属进行自由基加成或交叉偶联。相比之下，利用 3d 早期过渡金属进行光诱导 LMCT 提出了重大挑战。在此，我们描述了一种前所未有的烯丙型 C(sp 3 )–H 加成醛的方法，通过可见光诱导的 LMCT 采用铬 (Cr) 配合物作为催化剂。通过自由基捕获、动力学同位素效应 (KIE) 分析和瞬态吸收光谱等各种机理研究来研究反应途径，获得了宝贵的见解。所提出的机制表明溴自由基通过 Cr-Br 键的均裂发挥中介作用。值得注意的是，该协议扩展了我们对地球丰富的铬配合物的光化学性质的理解。
• The application of a mechanistic model leads to the extension of the Sharpless asymmetric dihydroxylation to allylic 4-methoxybenzoates and conformationally related amine and homoallylic alcohol derivatives.
  作者：E. J. Corey、Angel Guzman-Perez、Mark C. Noe

  DOI：10.1021/ja00149a003

  日期：1995.11

  The scope and utility of the Sharpless asymmetric dihydroxylation has been expanded to include the use of allylic 4-methoxybenzoates as precursors of a wide variety of substituted chiral glycerol derivatives. The allylic 4-methoxybenzoyl group was found to be superior to other allylic alcohol protecting groups with respect to both yield and enantiomeric purity of the product. For example, asymmetric dihydroxylation of allyl 4-methoxybenzoate (6a) using the (DHQD)(2)PYDZ . OsO4 (1 . OsO4) catalyst system affords (S)-3-(4-methoxybenzoyloxy)-1,2-propanediol (7a) in >99% yield and 98% ee. The 4-methoxybenzoates of a variety of other allylic alcohols also serve as excellent substrates, in contrast to the parent alcohols themselves. The efficient asymmetric dihydroxylation of homoallylic 4-methoxyphenyl ethers (12a and 15), allyl 9-fluorenimine (18b), bis(homoallyl) 4-methoxybenzoate (14) and other structurally related substrates is also described. This methodology was developed under mechanistic guidance from the transition state model advanced earlier by us for the bis-cinchona alkaloid catalyzed asymmetric dihydroxylation reaction. The 4-methoxybenzoyl group functions not only to selectively protect one of the hydroxy groups of the product triol for subsequent synthetic manipulation but also to provide an extended binding group that participates in hydrophobic and aryl-aryl interactions with the U-shaped binding pocket of the (DHQD)(2)PYDZ . OsO4 catalyst (1 . OsO4), thereby enhancing enantioselectivity.