(E)-tert-Butyl 5-(tert-Butyldimethylsiloxy)-2-pentenoate | 138877-98-2

• 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: (E)-tert-Butyl 5-(tert-Butyldimethylsiloxy)-2-pentenoate
• 英文别名: tert-butyl (E)-5-[(tert-butyldimethylsilyl)oxy]pent-2-enoate；(E)-tert-butyl 5-(tert-butyldimethylsilyloxy)pent-2-enoate；tert-butyl (E)-5-[tert-butyl(dimethyl)silyl]oxypent-2-enoate
• CAS: 138877-98-2
• 化学式: C₁₅H₃₀O₃Si
• 分子量: 286.487
• InChiKey: GCSKIZHGVLHFGC-PKNBQFBNSA-N

物化性质

• 沸点：
  312.8±25.0 °C(Predicted)
• 密度：
  0.908±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  19
• 可旋转键数：
  8
• 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：

  (E)-tert-Butyl 5-(tert-Butyldimethylsiloxy)-2-pentenoate 在 palladium dihydroxide 正丁基锂 、 ammonium formate 、 三氟乙酸 作用下， 以 乙醇 为溶剂， 反应 4.58h， 生成 3-(羧苯甲酰氨基)戊内酯
  参考文献：
  名称：

  An asymmetric ammonia synthon for Michael additions

  摘要：

  The highly diastereoselective 1,4-addition of lithiated chiral amine 1 to alpha,beta-unsaturated esters, followed by hydrogenolysis of the benzylic-type C-N bonds of the 1,4-adducts, provides an asymmetric ammonia synthon for Michael additions. Under optimized conditions, lithiated 1 adds to alpha,beta-unsaturated tert-butyl esters in dimethoxyethane at -63-degrees-C in high yield with very high diastereoselectivity. Small, large, functionalized, and chiral beta-ester substituents are amenable, with (S)-1 consistently adding to (E)-3 from the top as drawn in Table II. Hydrogenolysis liberates the beta-amino esters with typically 95-99% ee.

  DOI：

  10.1021/jo00033a037
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 1.42h， 生成 (E)-tert-Butyl 5-(tert-Butyldimethylsiloxy)-2-pentenoate
  参考文献：
  名称：

  An asymmetric ammonia synthon for Michael additions

  摘要：

  The highly diastereoselective 1,4-addition of lithiated chiral amine 1 to alpha,beta-unsaturated esters, followed by hydrogenolysis of the benzylic-type C-N bonds of the 1,4-adducts, provides an asymmetric ammonia synthon for Michael additions. Under optimized conditions, lithiated 1 adds to alpha,beta-unsaturated tert-butyl esters in dimethoxyethane at -63-degrees-C in high yield with very high diastereoselectivity. Small, large, functionalized, and chiral beta-ester substituents are amenable, with (S)-1 consistently adding to (E)-3 from the top as drawn in Table II. Hydrogenolysis liberates the beta-amino esters with typically 95-99% ee.

  DOI：

  10.1021/jo00033a037

文献信息

• A Stereospecific Alkene 1,2‐Aminofunctionalization Platform for the Assembly of Complex Nitrogen‐Containing Ring Systems
  作者：Yuxiang Zhu、Matthew J. S. Smith、Wenbin Tu、John F. Bower

  DOI：10.1002/anie.202301262

  日期：——

  activated N-Boc hydroxylamines triggers aminofunctionalization-based polycyclizations of tethered alkenes. The processes involve intramolecular stereospecific aza-Prilezhaev alkene aziridination in advance of stereospecific C−N cleavage by a pendant nucleophile. Using this approach, a wide range of alkene anti-1,2-difunctionalizations can be achieved.

  TFA 促进 O−Ts 的脱保护，激活的 N-Boc 羟胺触发基于氨基官能化的链烯烃多环化。该过程涉及分子内立体特异性氮杂-Prilezhaev 烯烃氮丙啶化，然后由悬垂亲核试剂进行立体特异性 C-N 裂解。使用这种方法，可以实现范围广泛的烯烃抗-1,2-双官能化。
• The Development of a Sulfamate-Tethered Aza-Michael Cyclization Allows for the Preparation of (−)-Negamycin <i>tert</i>-Butyl Ester
  作者：Harshit Joshi、Appasaheb K. Nirpal、Debobrata Paul、Steven P. Kelley、Joel T. Mague、Shyam Sathyamoorthi

  DOI：10.1021/acs.joc.4c00604

  日期：2024.4.19

  We present the first examples of intramolecular aza-Michael cyclizations of sulfamates and sulfamides onto pendant α,β-unsaturated esters, thioesters, amides, and nitriles. Stirring the substrate with catalytic quantities of the appropriate base delivers the product in good yield and excellent diastereoselectivity. The reactions are operationally simple, can be performed open to air, and are tolerant

  我们提出了氨基磺酸盐和磺酰胺在α,β-不饱和酯、硫酯、酰胺和腈侧链上的分子内氮杂迈克尔环化的第一个例子。用催化量的适当碱搅拌底物，可以得到良好产率和优异的非对映选择性的产物。该反应操作简单，可以在空气中进行，并且能够耐受多种重要的官能团。我们通过将其用于制备 (−)-negamycin 衍生物来强调该技术的实用性。
• Enantioselective Synthesis of α-Fluoro-β³-amino Esters: Synthesis of Enantiopure, Orthogonally Protected α-Fluoro-β³-lysine
  作者：Peter J. Duggan、Martin Johnston、Taryn L. March

  DOI：10.1021/jo101600c

  日期：2010.11.5

  The scope of a tandem conjugate addition fluorination sequence performed on alpha,beta-unsaturated esters using the enantiopure lithium amide derived from (S)-N-benzyl-N-(alpha-methylbenzyl)amine, and the electrophilic fluorinating agent N-fluorobenzenesulfonimide has been investigated. Using this method, a-fluoro-beta(3)-amino esters can be obtained in up to quantitative yield and 80:20 to >99:1 dr. This simple methodology does not rely on the use of alpha-amino acids from the chiral pool and thus provides the potential for the preparation of enantiopure alpha-fluoro-beta(3)-amino acids with a wide variety of side chains. Its utility was demonstrated through the synthesis of orthogonally protected (2S,3S)-alpha-fluoro-beta(3)-lysine.
• An asymmetric ammonia synthon for Michael additions
  作者：Joel M. Hawkins、Timothy A. Lewis

  DOI：10.1021/jo00033a037

  日期：1992.3

  The highly diastereoselective 1,4-addition of lithiated chiral amine 1 to alpha,beta-unsaturated esters, followed by hydrogenolysis of the benzylic-type C-N bonds of the 1,4-adducts, provides an asymmetric ammonia synthon for Michael additions. Under optimized conditions, lithiated 1 adds to alpha,beta-unsaturated tert-butyl esters in dimethoxyethane at -63-degrees-C in high yield with very high diastereoselectivity. Small, large, functionalized, and chiral beta-ester substituents are amenable, with (S)-1 consistently adding to (E)-3 from the top as drawn in Table II. Hydrogenolysis liberates the beta-amino esters with typically 95-99% ee.