tert-butyl triethylsilylglyoxylate | 852447-25-7

• 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 triethylsilylglyoxylate
• 英文别名: triethylsilyl glyoxylate；Tert-butyl 2-oxo-2-triethylsilylacetate
• CAS: 852447-25-7
• 化学式: C₁₂H₂₄O₃Si
• 分子量: 244.406
• InChiKey: UEYABJBDWBGSNH-UHFFFAOYSA-N

物化性质

• 沸点：
  272.5±23.0 °C(Predicted)
• 密度：
  0.929±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.94
• 重原子数：
  16
• 可旋转键数：
  7
• 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

反应信息

• 作为反应物：
  描述：

  tert-butyl triethylsilylglyoxylate 在 titanium(IV) isopropylate 、 乙基溴化镁 、 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 6.25h， 生成 (+/-)-(1R,4S,5R)-tert-butyl 1-hydroxy-3-methyl-5-nitro-4-pentylcyclopent-2-enecarboxylate
  参考文献：
  名称：

  通过甲硅烷基乙醛酸酯、乙酰化物和硝基烯烃的三组分偶联构建环戊醇衍生物

  摘要：

  Mg 乙炔化物、乙醛酸甲硅烷基酯和硝基烯烃的三组分偶联导致高度非对映选择性的 Kuwajima-Reich/vinylogous Michael 级联，提供四取代的甲硅烷氧基丙二烯产物。使用 DFT 计算研究了区域选择性和非对映选择性。这些甲硅烷氧基丙二烯通过独特的路易斯酸辅助亨利环化转化为环戊烯醇和环戊醇。环戊醇产物中存在的烯烃官能团可以使用非对映选择性酮羟基化反应进行加工。

  DOI：

  10.1021/ol2033527
• 作为产物：
  描述：

  Tert-butyl 2-diazo-2-triethylsilylacetate 在 Oxone 、 碳酸氢钠 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 0.25h， 以3.8 g的产率得到tert-butyl triethylsilylglyoxylate
  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

文献信息

• Symbiotic Reagent Activation:  Oppenauer Oxidation of Magnesium Alkoxides by Silylglyoxylates Triggers Second-Stage Aldolization
  作者：Xin Linghu、Andrew D. Satterfield、Jeffrey S. Johnson

  DOI：10.1021/ja062637+

  日期：2006.7.1

  alkoxide and Meerwein-Ponndorf-Verley reduction of the silylglyoxylate. The reduced silylglyoxylate undergoes subsequent [1,2]-Brook rearrangement and aldol reaction with the carbonyl oxidation product. The magnesium alkoxide may be accessed via deprotonation of primary or secondary alcohols with EtMgBr, via addition of Grignard reagents to aldehydes, or via CuI-catalyzed alkylation of epoxides. For aliphatic

  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。
• Diastereoselective Synthesis of Pentasubstituted γ-Butyrolactones from Silyl Glyoxylates and Ketones through a Double Reformatsky Reaction
  作者：Stephen N. Greszler、Jeffrey S. Johnson

  DOI：10.1002/anie.200900215

  日期：2009.5.4

  Three contiguous stereocenters can be established with remarkable diastereoselectivity in a double Reformatsky sequence. Densely functionalized γ‐butyrolactones were assembled rapidly by this approach, in which a ketone is used as the terminal electrophile (see scheme). Secondary transformations of the lactone products enhance their synthetic utility. R1=Me, H; R2=alkyl, aryl, CF3; Bn=benzyl, TBS=

  可以在双 Reformatsky 序列中以显着的非对映选择性建立三个连续的立体中心。通过这种方法可以快速组装密集官能化的 γ-丁内酯，其中使用酮作为末端亲电试剂（参见方案）。内酯产物的二次转化增强了它们的合成效用。R 1 =我，H；R 2 = 烷基、芳基、CF 3；Bn=苄基，TBS=叔丁基二甲基甲硅烷基。
• Three-Component Coupling Reactions of Silyl Glyoxylates, Vinyl Grignard Reagent, and Nitroalkenes: An Efficient, Highly Diastereoselective Approach to Nitrocyclopentanols
  作者：Gregory R. Boyce、Jeffrey S. Johnson

  DOI：10.1002/anie.201003470

  日期：2010.11.15

  easy: A regio‐ and stereoselective three‐component coupling reaction generates functionalized (Z)‐silyl enol ethers through a vinylation/[1,2]‐Brook rearrangement/vinylogous Michael reaction cascade. These adducts can then undergo a diastereoselective deprotection/intramolecular Henry sequence to rapidly assemble densely functionalized nitrocyclopentanols with three contiguous stereocenters (see scheme;

  快速简便：区域选择性和立体选择性三组分偶联反应通过乙烯基化/[1,2]-布鲁克重排/乙烯基迈克尔反应级联反应生成官能化的 ( Z )-甲硅烷基烯醇醚。然后，这些加合物可以进行非对映选择性脱保护/分子内亨利序列，以快速组装具有三个连续立体中心的密集官能化硝基环戊醇（参见方案；TES=三乙基甲硅烷基）。
• Catalytic Redox-Initiated Glycolate Aldol Additions of Silyl Glyoxylates
  作者：Stephen N. Greszler、Jeffrey S. Johnson

  DOI：10.1021/ol802828d

  日期：2009.2.19

  Lanthanide triisopropoxides catalyze a rapid, tandem MPV reduction/Brook rearrangement/aldol sequence between silyl glyoxylates and aldehydes that achieves catalytic turnover through alkoxide transfer from a strain-release Lewis acidic silacycle.
• Construction of Cyclopentanol Derivatives via Three-Component Coupling of Silyl Glyoxylates, Acetylides, and Nitroalkenes
  作者：Gregory R. Boyce、Shubin Liu、Jeffrey S. Johnson

  DOI：10.1021/ol2033527

  日期：2012.1.20

  The three-component coupling of Mg acetylides, silyl glyoxylates, and nitroalkenes results in a highly diastereoselective Kuwajima–Reich/vinylogous Michael cascade that provides tetrasubstituted silyloxyallene products. The regio- and diastereoselectivity were studied using DFT calculations. These silyloxyallenes were converted to cyclopentenols and cyclopentitols via a unique Lewis acid assisted Henry

  Mg 乙炔化物、乙醛酸甲硅烷基酯和硝基烯烃的三组分偶联导致高度非对映选择性的 Kuwajima-Reich/vinylogous Michael 级联，提供四取代的甲硅烷氧基丙二烯产物。使用 DFT 计算研究了区域选择性和非对映选择性。这些甲硅烷氧基丙二烯通过独特的路易斯酸辅助亨利环化转化为环戊烯醇和环戊醇。环戊醇产物中存在的烯烃官能团可以使用非对映选择性酮羟基化反应进行加工。