<2-(trimethylsilyl)ethyl>oxalyl chloride | 109862-07-9

• 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: <2-(trimethylsilyl)ethyl>oxalyl chloride
• 英文别名: 2-Trimethylsilylethyl 2-chloro-2-oxoacetate
• CAS: 109862-07-9
• 化学式: C₇H₁₃ClO₃Si
• 分子量: 208.717
• InChiKey: DADAPUAFAOJFDB-UHFFFAOYSA-N

物化性质

• 沸点：
  215.3±23.0 °C(Predicted)
• 密度：
  1.088±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.63
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  <2-(trimethylsilyl)ethyl>oxalyl chloride 在 copper(l) iodide 、 正丁基锂 、 18-冠醚-6 、 cesium fluoride 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 乙腈 为溶剂， 反应 10.0h， 生成 (Sp,Sc)-2-(trimethylsilyl)ethyl 3-<phosphinothioyl>-2-oxopropanoate
  参考文献：
  名称：

  Evidence for an intramolecular, stepwise reaction pathway for PEP phosphomutase catalyzed phosphorus-carbon bond formation

  摘要：

  The Tetrahymena pyriformis enzyme, phosphoenolpyruvate phosphomutase, catalyzes the rearrangement of phosphoenolpyruvate to the P-C bond containing metabolite, phosphonopyruvate. To distinguish between an intra- and intermolecular reaction pathway for this process an equimolar mixture of [P-O-18,C(2)-O-18]thiophosphonopyruvate and (all O-16) thiophosphonopyruvate was reacted with the phosphomutase, and the resulting products were analyzed by P-31 NMR. The absence of the cross-over product [C(2)-O-18]thiophosphonoenolpyruvate in the product mixture was interpreted as evidence for an intramolecular reaction pathway. To distinguish between a concerted and stepwise intramolecular reaction pathway the pure enantiomers of the chiral substrate [O-18]thiophosphonopyruvate were prepared and the stereochemical course of their conversion to chiral [O-18]thiophosphoenolpyruvate was determined. The assignments of the phosphorus configurations in the [O-18]thiophosphonopyruvate enantiomers reported earlier (McQueney, M. S.; Lee, S.-l.; Bowman, E.; Mariano, P. S.; Dunaway-Mariano, D. J. Am. Chem. Soc. 1989, 111, 6885-6887) were revised according to the finding that introduction of the O-18 label into the thiophosphonopyruvate precursor occurs with retention rather than with (the previously assumed) inversion of configuration. On the basis the observed conversion of (S(p))-[O-18]thiophosphonopyruvate to (S(p))-[O-18]thiophosphoenolpyruvate and (R(p))-[O-18]thiophosphonopyruvate to (Rp)-[O-18]thiophosphoenolpyruvate, it was concluded that the PEP phosphomutase reaction proceeds with retention of the phosphorus configuration and therefore by a stepwise mechanism. Lastly, the similar reactivity of the oxo- and thio-substituted phosphonopyruvate substrates (i.e., nearly equal V(max)) was interpreted to suggest that nucleophilic addition to the phosphorus atom is not rate limiting among the reaction steps.

  DOI：

  10.1021/jo00025a031
• 作为产物：
  描述：

  草酰氯 、 2-(三甲硅基)乙醇 反应 15.0h， 以62%的产率得到<2-(trimethylsilyl)ethyl>oxalyl chloride
  参考文献：
  名称：

  Evidence for an intramolecular, stepwise reaction pathway for PEP phosphomutase catalyzed phosphorus-carbon bond formation

  摘要：

  The Tetrahymena pyriformis enzyme, phosphoenolpyruvate phosphomutase, catalyzes the rearrangement of phosphoenolpyruvate to the P-C bond containing metabolite, phosphonopyruvate. To distinguish between an intra- and intermolecular reaction pathway for this process an equimolar mixture of [P-O-18,C(2)-O-18]thiophosphonopyruvate and (all O-16) thiophosphonopyruvate was reacted with the phosphomutase, and the resulting products were analyzed by P-31 NMR. The absence of the cross-over product [C(2)-O-18]thiophosphonoenolpyruvate in the product mixture was interpreted as evidence for an intramolecular reaction pathway. To distinguish between a concerted and stepwise intramolecular reaction pathway the pure enantiomers of the chiral substrate [O-18]thiophosphonopyruvate were prepared and the stereochemical course of their conversion to chiral [O-18]thiophosphoenolpyruvate was determined. The assignments of the phosphorus configurations in the [O-18]thiophosphonopyruvate enantiomers reported earlier (McQueney, M. S.; Lee, S.-l.; Bowman, E.; Mariano, P. S.; Dunaway-Mariano, D. J. Am. Chem. Soc. 1989, 111, 6885-6887) were revised according to the finding that introduction of the O-18 label into the thiophosphonopyruvate precursor occurs with retention rather than with (the previously assumed) inversion of configuration. On the basis the observed conversion of (S(p))-[O-18]thiophosphonopyruvate to (S(p))-[O-18]thiophosphoenolpyruvate and (R(p))-[O-18]thiophosphonopyruvate to (Rp)-[O-18]thiophosphoenolpyruvate, it was concluded that the PEP phosphomutase reaction proceeds with retention of the phosphorus configuration and therefore by a stepwise mechanism. Lastly, the similar reactivity of the oxo- and thio-substituted phosphonopyruvate substrates (i.e., nearly equal V(max)) was interpreted to suggest that nucleophilic addition to the phosphorus atom is not rate limiting among the reaction steps.

  DOI：

  10.1021/jo00025a031

文献信息

• Facile Preparation of Spirolactones by an Alkoxycarbonyl Radical Cyclization–Cross‐Coupling Cascade
  作者：Nicholas A. Weires、Yuriy Slutskyy、Larry E. Overman

  DOI：10.1002/anie.201903353

  日期：2019.6.17

  An alkoxycarbonyl radical cyclization–cross‐coupling cascade has been developed that allows functionalized γ‐butyrolactones to be prepared in one step from simple tertiary alcohol‐derived homoallylic oxalate precursors. The reaction succeeds with aryl and vinyl electrophiles and is compatible with heterocyclic fragments in both coupling partners. This chemistry allows for the rapid construction of

  已开发出烷氧基羰基自由基环化-交叉偶联级联反应，可从简单的叔醇衍生的均芳草酸均聚物前体一步制备官能化的γ-丁内酯。该反应在芳基和乙烯基亲电子试剂上成功完成，并且与两个偶联配偶体中的杂环片段均相容。这种化学性质使得螺内酯的快速构建成为可能，这在药物开发中很有意义。
• Alkylphosphonous acid diesters, novel reagents for the oxalimide cyclization to penems
  作者：K.-H. Budt、G. Fischer、R. Hörlein、R. Kirrstetter、R. Lattrell

  DOI：10.1016/s0040-4039(00)79085-x

  日期：1992.9

  Alkylphosphonous acid diesters MeP(OR)23a-b were shown to be highly effctive and mild reducing reagents in the oxalimide cyclization of azetidinone-1-oxalyl-4-di- or tri-thiocarbonates or 4-thioesters1a-t forming penems 2a-t at lower temperature shorter reaction times, and higher yields compared to classical phosphites P(OMe)3 and P(OEt)3.

  烷基亚膦酸二酯MeP（OR）2 3a-b在氮杂环丁酮-1-草酰-4-二-或三硫代碳酸酯或4-硫酯1a-t生成青霉烯2a-t的草酰亚胺环化反应中显示出高效率和温和的还原剂与传统的亚磷酸酯P（OMe）3和P（OEt）3相比，在较低的温度下t的反应时间更短，产率更高。
• N-Acylation of 4-alkylidene-β-lactams: unexpected results
  作者：Gianfranco Cainelli、Daria Giacomini、Massimo Gazzano、Paola Galletti、Arianna Quintavalla

  DOI：10.1016/s0040-4039(03)01533-8

  日期：2003.8

  This paper describes the different reactivity of E- and Z-4-alkylidene-β-lactams in acylation reactions under basic conditions. The E isomer is readily acylated, whereas the Z reacted sluggishly rearranging to the corresponding oxazin-6-one. The N-acylation of Z isomers was successfully obtained with oxalyl- or malonyl chlorides in benzene at reflux.

  本文描述了碱性条件下E-和Z -4-亚烷基-β-内酰胺在酰化反应中的不同反应性。该ë异构体很容易酰化，而ž反应的缓慢重排以相应的恶嗪-6-酮。用苯中的草酰氯或丙二酰氯在回流下成功获得Z异构体的N-酰化。
• Total Synthesis of Rameswaralide Utilizing a Pharmacophore-Directed Retrosynthetic Strategy
  作者：Nathanyal J. Truax、Safiat Ayinde、Jun O. Liu、Daniel Romo

  DOI：10.1021/jacs.2c08245

  日期：2022.10.12

  to the first total synthesis of the cembranoid rameswaralide in order to simultaneously achieve a total synthesis while also developing a structure–activity relationship profile throughout the synthetic effort. The synthesis utilized a Diels–Alder lactonization process, including a rare kinetic resolution to demonstrate the potential of this strategy for an enantioselective synthesis providing both

  将药效团导向的逆合成策略应用于 cembranoid rameswaralide 的第一次全合成，以同时实现全合成，同时在整个合成过程中建立结构-活性关系谱。该合成利用 Diels-Alder 内酯化过程，包括罕见的动力学拆分，以证明该策略在对映选择性合成中的潜力，可提供 5,5,6- 和通过扩环获得 5,5,7-三环存在于几个Sinularia中的系统软珊瑚 cembranoids。一种关键的合成中间体，一种三环环氧α-溴环庚烯酮，对 HCT-116 结肠癌细胞系表现出高细胞毒性和有趣的选择性。该中间体实现了三种独特的 D 环环化策略，包括光催化的分子内 Giese 型自由基环化和非对映选择性、分子内烯胺介导的迈克尔加成，后者环化构建最终的 D 环以提供 rameswaralide。偶然发现三环环氧环庚烯酮的氧化态转位通过假定的双乙烯系 E1 型消除进行，从而能够轻松引入所需的 α-亚甲基丁内酯。rameswaralide
• Total Synthesis of the Diterpenes (+)-Randainin D and (+)-Barekoxide via Photoredox-Catalyzed Deoxygenative Allylation
  作者：Oleksandr Vyhivskyi、Olivier Baudoin

  DOI：10.1021/jacs.4c02224

  日期：——

  We report the first enantioselective total synthesis of diterpenoid randainin D, which possesses a hydroazulenone core with a β-substituted butenolide moiety on the cycloheptane ring. The trans-5/7 ring system was formed via a highly challenging ring-closing metathesis delivering the tetrasubstituted cycloheptenone. The butenolide moiety was installed via a novel deoxygenative allylation under Ir-photoredox

  我们报道了二萜 randainin D 的第一个对映选择性全合成，它具有氢薁酮核心，环庚烷环上有 β-取代的丁烯内酯部分。反式-5/7环系统是通过极具挑战性的闭环复分解形成的，从而产生四取代的环庚烯酮。使用草酸甲酯作为 red/ox 标签，在 Ir-光氧化还原催化下通过新型脱氧烯丙基化安装丁烯酸内酯部分。此外，所开发的烯丙基化已成功用于(+)-barek盐的7步全合成。这项研究表明，这种脱氧烯丙基化方法是在天然产物合成中形成 Cq-C(sp 3 ) 键（Cq = 四元中心）的一种有前景的策略。