tert-butyl tert-butyldimethylsilylglyoxylate | 852447-17-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: tert-butyl tert-butyldimethylsilylglyoxylate
• 英文别名: tert-butyl 2-(tert-butyldimethylsilyl)-2-oxoacetate；Tert-butyl (tert-butyldimethylsilyl)glyoxylate；tert-butyl 2-[tert-butyl(dimethyl)silyl]-2-oxoacetate
• CAS: 852447-17-7
• 化学式: C₁₂H₂₄O₃Si
• 分子量: 244.406
• InChiKey: GGYHTNUVBJRLDM-UHFFFAOYSA-N

物化性质

• 沸点：
  263.7±23.0 °C(Predicted)
• 密度：
  0.920 g/mL at 25 °C
• 闪点：
  88℃

计算性质

• 辛醇/水分配系数(LogP)：
  2.94
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• WGK Germany：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl tert-butyldimethylsilylglyoxylate 在 camphor-10-sulfonic acid 、 乙基溴化镁 作用下， 以 四氢呋喃 为溶剂， 反应 48.25h， 生成 2,2-dimethyl-5-(pent-4-enyl)-[1,3]dioxolane-4-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  共生试剂活化：甲硅烷基乙醛酸盐对镁醇盐的 Oppenauer 氧化触发第二阶段醛醇化

  摘要：

  在环境温度下用醇镁处理甲硅烷基乙醛酸导致醇盐的共生 Oppenauer 氧化和甲硅烷基乙醛酸的 Meerwein-Ponndorf-Verley 还原。还原的甲硅烷基乙醛酸酯随后与羰基氧化产物发生 [1,2]-布鲁克重排和羟醛反应。醇镁可以通过伯醇或仲醇与 EtMgBr 的去质子化、通过将格氏试剂添加到醛中或通过 CuI 催化的环氧化物烷基化来获得。对于脂肪族伯醇盐，观察到中等水平的抗非对映选择。交叉实验表明，新生醛从镁中心的解离速度快于 [1,2]-布鲁克重排和醛醇化。

  DOI：

  10.1021/ja062637+
• 作为产物：
  描述：

  重氮基乙酸叔丁酯 在 Oxone 、 碳酸氢钠 、 N,N-二异丙基乙胺 作用下， 以 乙醚 、 二氯甲烷 、 丙酮 为溶剂， 反应 16.25h， 生成 tert-butyl tert-butyldimethylsilylglyoxylate
  参考文献：
  名称：

  Three-Component Coupling Reactions of Silylglyoxylates, Alkynes, and Aldehydes:  A Chemoselective One-Step Glycolate Aldol Construction

  摘要：

  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.

  DOI：

  10.1021/ja043884l
• 作为试剂：
  描述：

  、 (R,E)-2-methyl-N-(phenylmethylene)-2-propanesulfinamide 在 tert-butyl tert-butyldimethylsilylglyoxylate 作用下， 生成 S-phenyl 3-(((R)-tert-butylsulfinyl)amino)-3-phenylpropanethioate
  参考文献：
  名称：

  Three-Component Reactions of Sulfonylimidates, Silyl Glyoxylates and N-tert-Butanesulfinyl Aldimines: An Efficient, Diastereoselective, and Enantioselective Synthesis of Cyclic N-Sulfonylamidines

  摘要：

  Three-component coupling reactions of sulfonylimidates, silyl glyoxylates and N-tert-butanesulfinyl aldimines efficiently provide cyclic N-sulfonylamiclines containing free endocyclic N-H. The formation of two C-C bonds (contiguous stereogenic carbons), one O-Si bond, and one C-N bond, together with the cleavage of the chiral auxiliary (tert-butanesulfinyl group), occurs with excellent chemoselectivity, diastereoselectivity, and enantioselectivity in this one-pot cascade transformation.

  DOI：

  10.1021/ol201029b

文献信息

• “On Water” Direct Catalytic Vinylogous Aldol Reaction of Silyl Glyoxylates
  作者：Hong Pan、Man-Yi Han、Pinhua Li、Lei Wang

  DOI：10.1021/acs.joc.9b01945

  日期：2019.11.1

  The unique reactivity of water in the direct catalytic vinylogous aldol reaction of silyl glyoxylates is reported. With the hydrogen-bonding networks from water, the unfavorable homogeneous reactions in organic solvents were severely suppressed, and the "on water" relay chemistry for the vinylogous aldol reaction was realized in heterogeneous conditions (water as solvent), providing the desired α-hydroxysilanes

  据报道，在乙醛酸甲硅烷基酯的直接催化乙烯基醇醛醇醛反应中，水具有独特的反应性。通过水与氢的键合网络，可以严重抑制有机溶剂中不利的均相反应，并且在非均相条件下（水为溶剂）实现了乙烯基醇醛醇缩醛反应的“水上”中继化学反应，从而提供了所需的α-羟基硅烷具有高产的季碳中心。此外，还展示了对水在生物系统中作用的新见解。
• Catalytic asymmetric addition of thiols to silyl glyoxylates for synthesis of multi-hetero-atom substituted carbon stereocenters
  作者：Mingming Guan、Shiyu Wang、Yao Luo、Weidi Cao、Xiaohua Liu、Xiaoming Feng

  DOI：10.1039/d1sc01096d

  日期：——

  A chiral Lewis acid-catalyzed enantioselective addition of thiols to silyl glyoxylates was developed. The reaction proceeds well with a broad range of thiols and acylsilanes, affording the target tertiary chiral α-silyl–α-sulfydryl alcohols with multi-hetero-atom carbon stereocenters in excellent yields (up to 99%) and enantioselectivities (up to 98% ee). A series of control experiments were conducted

  开发了手性路易斯酸催化的巯基对乙氧基化甲硅烷基化物的对映选择性加成。反应可与多种硫醇和酰基硅烷一起进行，使目标叔级手性α-甲硅烷基-α-巯基醇与多杂原子碳立构中心形成，并具有出色的收率（高达99％）和对映选择性（高达98％） ee）。进行了一系列对照实验以阐明反应机理。
• Remote Stereoinduction in the Acylation of Fully Substituted Enolates: Tandem Reformatsky/Quaternary Claisen Condensations of Silyl Glyoxylates and β-Lactones
  作者：Stephen N. Greszler、Justin T. Malinowski、Jeffrey S. Johnson

  DOI：10.1021/ja108848d

  日期：2010.12.15

  glyoxylates and β-lactones to give highly functionalized Claisen condensation products. A heretofore undocumented instance of stereochemical 1,4-induction results in efficient transmission of β-lactone stereochemistry to the emerging fully substituted stereocenter. Second-stage transformations reveal that the five heteroatom-containing functionalities embedded within the products are entirely chemo-differentiated

  Reformatsky 试剂依次与乙醛酸甲硅烷基酯和 β-内酯反应，得到高度官能化的克莱森缩合产物。迄今为止未记录的立体化学 1,4-诱导实例导致 β-内酯立体化学有效传输到新兴的完全取代的立体中心。第二阶段的转化表明，嵌入产品中的五个含杂原子的功能是完全化学分化的，这种情况允许快速组装 leustroducsin B 核心亚结构。
• Hydrogen-Bond-Assisted Sequential Reaction of Silyl Glyoxylates: Stereoselective Synthesis of Silyl Enol Ethers
  作者：Chen Zhu、Man-Yi Han、Xiu-Xia Liang、Bin Guan、Pinhua Li、Lei Wang

  DOI：10.1021/acs.orglett.0c03683

  日期：2021.1.1

  A novel hydrogen-bond-assisted sequential reaction of silyl glyoxylates is described. This method provides an efficient strategy for the synthesis of silyl enol ethers with high selectivity. In these transformations, hydrogen bonds from 2-nitroethanol and its derivatives are critical to the stereochemical outcome. Both E- and Z-isomers are achieved via Henry reaction/Brook rearrangement/elimination

  描述了一种新型的氢键辅助的乙醛酸甲硅烷基酯的顺序反应。该方法为合成高选择性的甲硅烷基烯醇醚提供了有效的策略。在这些转化中，2-硝基乙醇及其衍生物的氢键对于立体化学结果至关重要。既ë -和ž 1： -异构体通过Henry反应/重排布鲁克/消除和亨利反应/重排布鲁克/复古亨利反应/消除过程，分别为（最多99实现Ž -选择性，和9.2：1 È -选择性）。
• Highly Efficient Access to Both Geometric Isomers of Silyl Enol Ethers: Sequential 1,2-Brook/Wittig Reactions
  作者：Yuji Matsuya、Kentaro Wada、Daishiro Minato、Kenji Sugimoto

  DOI：10.1002/anie.201604945

  日期：2016.8.16

  2‐Brook/Wittig reactions were developed for the preparation of silyl enol ethers. This method enables highly selective preparation of both geometric isomers of glyoxylate silyl enol ethers, using aldehydes (E‐selective) and tosylimines (Z‐selective) as a Wittig electrophile. The salt‐free conditions of this reaction system are likely to be advantageous for switching the selectivity. The optimal reaction conditions

  开发了新的顺序1,2-Brook / Wittig反应，用于制备甲硅烷基烯醇醚。通过使用醛（E选择性）和甲苯磺胺（Z选择性）作为维蒂希亲电子试剂，该方法能够高度选择性地制备乙醛酸甲硅烷基烯醇醚的两种几何异构体。该反应系统的无盐条件可能对切换选择性有利。研究了最佳反应条件和反应的一般性，并讨论了观察到的选择性的合理解释。