4-acetoxy-1-trimethylsilylazetidin-2-one | 80675-59-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: 4-acetoxy-1-trimethylsilylazetidin-2-one
• 英文别名: 4-Oxo-1-(trimethylsilyl)azetidin-2-yl acetate；(4-oxo-1-trimethylsilylazetidin-2-yl) acetate
• CAS: 80675-59-8
• 化学式: C₈H₁₅NO₃Si
• 分子量: 201.297
• InChiKey: YLHRLXYVOALTRG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.94
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(三甲基硅氧基)丙烯 、 4-acetoxy-1-trimethylsilylazetidin-2-one 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 1.75h， 生成
  参考文献：
  名称：

  SmI₂-Mediated Cyclizations of Derivatized β-Lactams for the Highly Diastereoselective Construction of Functionalized Prolines

  摘要：

  A series of C4-keto-functionalized 1-[(benzoyloxy)(ethoxycarbonyl)methyl]-2-azetidinones were prepared and studied for their tendency to undergo a Reformatsky-type cyclization to fused bicyclic or tricyclic beta-lactams with the single-electron reducing agent samarium diiodide. Whereas the azetidinone 21a underwent reductive cyclization, affording the potent antibiotic sanfetrinem's tricyclic [4.5.6] core structure as the major component, all other examples tested resulted in cyclization followed by an N to O acyl migration involving cleavage of the beta-lactam ring as the favored pathway. Highly functionalized proline derivatives were therefore accessed as single diastereomers through the reductive cyclization of benzoates 21b, 22, 23a,b, 24b, and 25-28. Pertinent for the success of these cyclizations was the addition of 1 equiv of tert-butyl alcohol, allowing for the protonation of the basic amide derivative obtained after the acyl migration step. The diastereoselectivities of these reactions deviate from those of similar cyclizations involving the corresponding lithium enolate. This divergence could be rationalized by the coordination of the metal ion of the samarium(III) enolate intermediate to the beta-lactam amide functionality in the cyclization step, which may not be possible for lithium enolates.

  DOI：

  10.1021/jo0104983
• 作为产物：
  描述：

  三甲基氯硅烷 、 4-乙酰氧基-2-氮杂环丁酮 在 三乙胺 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以90%的产率得到4-acetoxy-1-trimethylsilylazetidin-2-one
  参考文献：
  名称：

  Convenient synthesis of .alpha.-(2-oxoazetidin-4-yl) esters and ketones and related systems

  摘要：

  DOI：

  10.1021/jo00184a001

文献信息

• Synthesis of esters of the potent anti-bacterial trinems and analogues
  作者：P. Mark Jackson、Stanley M. Roberts、Silvia Davalli、Daniele Donati、Carla Marchioro、Alcide Perboni、Stefano Proviera、Tino Rossi

  DOI：10.1039/p19960002029

  日期：——

  Coupling the silyl enol ether 5 and the β-lactam 9(R = Me3Si) affords the ketones 13a–d. Compounds 13a, 13c and 13d are converted into the tricyclic lactams 16–20, 23–25. (Chemoenzymatic synthesis of optically pure silyl enol ether 5 gave access to homochiral lactams 23–25.) In addition the ketoazetidinones 13 are protected as the 1,3-oxazanes 30. A hydroxyethyl moiety is introduced into these oxazanes

  甲硅烷基烯醇醚5和β-内酰胺9（R = Me 3 Si）偶联得到酮13a-d。化合物13a，13c和13d转化为三环内酰胺16-20、23-25。（光学纯的甲硅烷基烯醇醚5的化学酶法合成可得到同手性内酰胺23-25。）此外，酮氮杂环丁酮13被保护为1,3-恶唑烷30。使用Bouffard方法进行所需的立体化学反应，得到醇32。形成相应的碳酸硝基苄酯，脱保护和氧化提供了酮35a和35b，其随后分别转化为三苯甲基41a和41b。
• Concise syntheses of 4-(arylcarbonylmethyl)-azetidin-2-ones and related systems
  作者：Anthony G. M. Barrett、Peter Quayle

  DOI：10.1039/c39810001076

  日期：——

  On catalysis by trimethylsilyl trifluoromethane-sulphonate, 4-acetoxy-1-trimethylsilylazetidin-2-one reacted with the enol silanes [R1CHC(OSiMe3)R2] to give the β-lactams [[graphic omitted]HCH(R1)COR2] in excellent yields (71 to 95%).

  在三甲基甲硅烷基三氟甲烷磺酸酯的催化下，4-乙酰氧基-1-三甲基甲硅烷基氮杂环丁烷-2-one与烯醇硅烷[R 1 CH C（OSiMe 3）R 2 ]反应，得到β-内酰胺[[略图] HCH（R）1）COR 2 ]，收率极高（71％至95％）。
• Vinylic Halogenation in 4-Alkylidenazetidin-2-ones
  作者：Gianfranco Cainelli、Paola Galletti、Daria Giacomini、Sebastiano Licciulli、Arianna Quintavalla

  DOI：10.1002/ejoc.200601095

  日期：2007.5

  The synthesis of a new family of halogenated β-lactams by oxidative substitution of vinylic hydrogen in conjugated double bonds of 4-alkylidenazetidinones is reported. Optimised procedures give good to excellent yields of chloro, bromo, iodo and nitro derivatives. A mechanism to explain the direct vinylic substitution is proposed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  报道了通过氧化取代 4-亚烷基氮杂环丁酮共轭双键中的乙烯基氢来合成新的卤代 β-内酰胺家族。优化的程序使氯代、溴代、碘代和硝基衍生物的产率从高到高。提出了一种解释直接乙烯基取代的机制。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• BARRETT, A. G. M.;QUAYLE, P., J. CHEM. SOC. CHEM. COMMUN., 1981, N 20, 1076-1077
  作者：BARRETT, A. G. M.、QUAYLE, P.

  DOI：——

  日期：——
• SmI₂-Mediated Cyclizations of Derivatized β-Lactams for the Highly Diastereoselective Construction of Functionalized Prolines
  作者：Mikkel F. Jacobsen、Maris Turks、Rita Hazell、Troels Skrydstrup

  DOI：10.1021/jo0104983

  日期：2002.4.1

  A series of C4-keto-functionalized 1-[(benzoyloxy)(ethoxycarbonyl)methyl]-2-azetidinones were prepared and studied for their tendency to undergo a Reformatsky-type cyclization to fused bicyclic or tricyclic beta-lactams with the single-electron reducing agent samarium diiodide. Whereas the azetidinone 21a underwent reductive cyclization, affording the potent antibiotic sanfetrinem's tricyclic [4.5.6] core structure as the major component, all other examples tested resulted in cyclization followed by an N to O acyl migration involving cleavage of the beta-lactam ring as the favored pathway. Highly functionalized proline derivatives were therefore accessed as single diastereomers through the reductive cyclization of benzoates 21b, 22, 23a,b, 24b, and 25-28. Pertinent for the success of these cyclizations was the addition of 1 equiv of tert-butyl alcohol, allowing for the protonation of the basic amide derivative obtained after the acyl migration step. The diastereoselectivities of these reactions deviate from those of similar cyclizations involving the corresponding lithium enolate. This divergence could be rationalized by the coordination of the metal ion of the samarium(III) enolate intermediate to the beta-lactam amide functionality in the cyclization step, which may not be possible for lithium enolates.