1,1-dimethylethyl 3-(((1,1-dimethylethyl)dimethylsilyl)oxy)-2-methylenebutanoate | 166763-09-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 1,1-dimethylethyl 3-(((1,1-dimethylethyl)dimethylsilyl)oxy)-2-methylenebutanoate
• 英文别名: Tert-butyl 3-[tert-butyl(dimethyl)silyl]oxy-2-methylidenebutanoate
• CAS: 166763-09-3
• 化学式: C₁₅H₃₀O₃Si
• 分子量: 286.487
• InChiKey: WZQVKOTXMAYROZ-UHFFFAOYSA-N

物化性质

• 沸点：
  308.1±25.0 °C(Predicted)
• 密度：
  0.903±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.29
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,1-dimethylethyl 3-(((1,1-dimethylethyl)dimethylsilyl)oxy)-2-methylenebutanoate 在 4-二甲氨基吡啶 、 正丁基锂 、 四丁基氟化铵 、 水 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 苯 为溶剂， 生成 (2R,3S)-3-Acetoxy-2-ethylsulfanylmethyl-butyric acid
  参考文献：
  名称：

  通过将硫醇立体选择性共轭加成到Baylis-Hillman加合物中，可以简单地制备β-羟基-α-硫代甲基羰基化合物

  摘要：

  在催化量的硫醇锂存在下，硫醇向Baylis-Hillman加合物的亲核加成反应顺利进行，从而立体选择性地生成顺式-β-羟基-α-硫代甲基羰基化合物。

  DOI：

  10.1016/s0040-4039(02)01318-7
• 作为产物：
  描述：

  tert-butyl 3-hydroxy-2-methylenebutanoate 、 叔丁基二甲基氯硅烷 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以69%的产率得到1,1-dimethylethyl 3-(((1,1-dimethylethyl)dimethylsilyl)oxy)-2-methylenebutanoate
  参考文献：
  名称：

  A Simple Route to .alpha.-Substituted-.beta.-Amino Ester Precursors of Carbapenem Antibiotics

  摘要：

  A three-step process is presented for the preparation of alpha-substituted-beta-amino esters which can serve as precursors to a key intermediate in carbapenem synthesis. The pivotal reaction in this sequence involves a highly diastereoselective conjugate addition reaction. Two series of alkenoates bearing a stereogenic substituent attached to C2 were prepared and their conjugate addition reactions with benzylamine studied under several different sets of conditions. Conjugate addition of benzylamine to alkenoates 7a and 7d, in methanol at room temperature, gave adducts 8a and Sd with virtually complete anti-diastereoselectivity. These two beta-amino esters bear the correct relative stereochemistry and side chain to serve as precursors for carbapenem antibiotic synthetic intermediates. The role of the allylic substituents of the alkenoates 7a-e in determining the stereochemical outcome of these additions is discussed. These conjugate additions were explored further by the preparation and conjugate addition reactions of the alpha,beta-disubstituted alkenoates 15a and 15b. It was found that the presence of a beta-substituent led to a dramatic reduction in yield although the same anti-diastereoselectivity was maintained. The relative stereochemistry of the adducts was established by examination of the relevant coupling constants in the H-1 NMR spectra of their tetrahydro-1,3-oxazine derivatives.

  DOI：

  10.1021/jo00125a043

文献信息

• Simple preparation of β-hydroxy-α-thiomethyl carbonyl compounds via stereoselective conjugate addition of thiol to Baylis–Hillman adducts
  作者：Akio Kamimura、Rie Morita、Kenji Matsuura、Yoji Omata、Masashi Shirai

  DOI：10.1016/s0040-4039(02)01318-7

  日期：2002.8

  Nucleophilic addition of thiols to Baylis–Hillman adducts smoothly proceeded in the presence of catalytic amounts of lithium thiolate to give syn-β-hydroxy-α-thiomethyl carbonyl compounds stereoselectively.

  在催化量的硫醇锂存在下，硫醇向Baylis-Hillman加合物的亲核加成反应顺利进行，从而立体选择性地生成顺式-β-羟基-α-硫代甲基羰基化合物。
• Acyclic Stereocontrol of Free Radical Reactions Involving Alkyl 2-(1-Hydroxyalkyl)propenoates
  作者：FW Eastwood、RD Mifsud、P Perlmutter

  DOI：10.1071/ch9942187

  日期：——

  The addition of cyclohexyl and t-butyl free radicals to silylated derivatives of alkyl 2-(1-hydroxyalkyl) propenoates was found to be stereoselective . In the case of the cyclohexyl radical the stereoselectivity was dependent upon the conditions used to generate the free radical and to quench the intermediate. Stereoselectivity in additions of the t-butyl radical was found to be temperature-dependent. In all cases stereoselectivity increased as the steric bulk of the group attached to the carbinol oxygen increased. A simple model which accounts for the stereoselectivity is proposed.

  研究发现，环己基和叔丁基自由基与 2-（1-羟基烷基）丙烯酸烷基硅烷化衍生物的加成具有立体选择性。环己基自由基的立体选择性取决于生成自由基和淬灭中间体的条件。研究发现，t-丁基自由基加成的立体选择性与温度有关。在所有情况下，立体选择性都会随着连接到羰基氧上的基团立体体积的增加而增加。提出了一个解释立体选择性的简单模型。
• Eastwood Frank W., Mifsud Roger D., Perlmutter Patrick, Austral. J. Chem., 47 (1994) N 12, S 2187-2200
  作者：Eastwood Frank W., Mifsud Roger D., Perlmutter Patrick

  DOI：——

  日期：——
• A Simple Route to .alpha.-Substituted-.beta.-Amino Ester Precursors of Carbapenem Antibiotics
  作者：Patrick Perlmutter、Mark Tabone

  DOI：10.1021/jo00125a043

  日期：1995.10

  A three-step process is presented for the preparation of alpha-substituted-beta-amino esters which can serve as precursors to a key intermediate in carbapenem synthesis. The pivotal reaction in this sequence involves a highly diastereoselective conjugate addition reaction. Two series of alkenoates bearing a stereogenic substituent attached to C2 were prepared and their conjugate addition reactions with benzylamine studied under several different sets of conditions. Conjugate addition of benzylamine to alkenoates 7a and 7d, in methanol at room temperature, gave adducts 8a and Sd with virtually complete anti-diastereoselectivity. These two beta-amino esters bear the correct relative stereochemistry and side chain to serve as precursors for carbapenem antibiotic synthetic intermediates. The role of the allylic substituents of the alkenoates 7a-e in determining the stereochemical outcome of these additions is discussed. These conjugate additions were explored further by the preparation and conjugate addition reactions of the alpha,beta-disubstituted alkenoates 15a and 15b. It was found that the presence of a beta-substituent led to a dramatic reduction in yield although the same anti-diastereoselectivity was maintained. The relative stereochemistry of the adducts was established by examination of the relevant coupling constants in the H-1 NMR spectra of their tetrahydro-1,3-oxazine derivatives.
• A convenient stereoselective synthesis of β-lactams from β-hydroxy-α-thioalkylesters prepared from Michael/aldol tandem reaction or stereoselective addition of thiols to the Baylis–Hillman adducts
  作者：Akio Kamimura、Rie Morita、Kenji Matsuura、Hiromasa Mitsudera、Masashi Shirai

  DOI：10.1016/j.tet.2003.10.035

  日期：2003.12

  A convenient stereoselective synthesis of β-lactams from thio-Michael/aldol tandem adduct is described. syn-Selective tandem reaction followed by amidation and intramolecular SN2 reaction provided β-lactams in diastereomerically pure form. The tandem reaction with aliphatic aldehydes, on the other hand, afforded a mixture of diastereomers of corresponding tandem adducts in about 3:1 ratio so that the

  描述了由硫代迈克尔-迈克尔/醛醇双键加合物方便地立体选择性合成β-内酰胺。syn-选择性串联反应，然后进行酰胺化和分子内S N 2反应，提供非对映体纯形式的β-内酰胺。另一方面，与脂族醛的串联反应以约3∶1的比例提供了相应的串联加合物的非对映异构体的混合物，使得转化为β-内酰胺提供了非对映异构体的混合物。作为制备串联加合物的另一种方法，开发了将脂肪族硫醇立体选择性迈克尔加成到Baylis-Hillman加合物中的方法。立体选择性对羟基上的保护基敏感，TBS保护带来了最成功的合成选择性形成串联加合物。该方法可用于Baylis-Hillman加合物的酮衍生物，但未观察到腈-Baylis-Hillman加合物的选择性。加合物的类似转化立体选择性地提供了所需的β-内酰胺。