methyl trimethylsilyl dimethylketene acetal | 55499-73-5

• 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: methyl trimethylsilyl dimethylketene acetal
• 英文别名: Methyl-2-methyl-2-(trimethylsilyl)-propionat；Methyl 2-methyl-2-trimethylsilylpropanoate
• CAS: 55499-73-5
• 化学式: C₈H₁₈O₂Si
• 分子量: 174.315
• InChiKey: BSCFLWPNFDJWBS-UHFFFAOYSA-N

物化性质

• 沸点：
  160.7±13.0 °C(Predicted)
• 密度：
  0.872±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.28
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl trimethylsilyl dimethylketene acetal 、 (2-methyl-3-oxo-1H-isoindol-1-yl) acetate 在 三甲基氯硅烷 、 1,3-bis(2,4,6-trimethylphenyl)-2-iodoimidazolium triflate 作用下， 以 氯仿 为溶剂， 反应 24.0h， 以77%的产率得到
  参考文献：
  名称：

  Halogen-Bond-Catalyzed Addition of Carbon-Based Nucleophiles to N-Acylimminium Ions

  摘要：

  N-acylimminium ions are an important class of synthetic intermediates to produce diverse products upon treatment with different nucleophiles. Most of the reported catalytic protocol involved moisture-sensitive Lewis acids or transition metal. Herein, we reported an organocatalytic version by using halogen-bond catalyst as mild Lewis acid through anion-abstraction strategy. A preliminary result of enantioselective version by employing a chiral BINOL-phosphate anion has also been demonstrated.

  DOI：

  10.1021/acs.orglett.9b02006
• 作为产物：
  描述：

  (三甲基硅基)乙酸甲酯 、 碘甲烷 生成 methyl trimethylsilyl dimethylketene acetal
  参考文献：
  名称：

  Zaitseva,G.S. et al., Journal of general chemistry of the USSR, 1975, vol. 45, p. 78 - 80

  摘要：

  DOI：

文献信息

• Switching between <i>X</i>-Pyrano-, <i>X</i>-Furano-, and Anhydro-<i>X</i>-pyranoside Synthesis (X = C, N) under Lewis acid Catalyzed Conditions
  作者：Youngran Seo、Jared M. Lowe、Neyen Romano、Michel R. Gagné

  DOI：10.1021/acs.orglett.1c01713

  日期：2021.8.6

  A variety of C-glycosides can be obtained from the fluoroarylborane (B(C6F5)3) or silylium (R3Si+) catalyzed functionalization of 1-MeO- and per-TMS-sugars with TMS-X reagents. A one-step functionalization with a change as simple as the addition order and/or Lewis acid and TMS-X enables one to afford chiral synthons that are common (C-pyranosides), have few viable synthetic methods (C-furanosides)

  各种C-糖苷可以从氟芳基硼烷(B(C 6 F 5 ) 3 )或硅基(R 3 Si + )催化的1-MeO-和全TMS-糖与TMS-X试剂的官能化获得。一步功能化只需简单地改变加成顺序和/或路易斯酸和 TMS-X，即可获得常见的手性合成子（ C-吡喃糖苷），但几乎没有可行的合成方法（ C-呋喃糖苷），或实际上是未知的（脱水-C-吡喃糖苷），其机械地分别由是否发生直接取代、异构化/取代或取代/异构化而产生。
• Visible-light-accelerated amination of quinoxalin-2-ones and benzo[1,4]oxazin-2-ones with dialkyl azodicarboxylates under metal and photocatalyst-free conditions
  作者：Jaume Rostoll-Berenguer、Murta Capella-Argente、Gonzalo Blay、José R. Pedro、Carlos Vila

  DOI：10.1039/d1ob01157j

  日期：——

  A direct sp3 C–H amination of cyclic amines (dihydroquinoxalinones and dihydrobenzoxazinones) with dialkyl azo dicarboxylates accelerated by visible-light irradiation under metal and photocatalyst-free conditions is described. This protocol features very mild reaction conditions for the synthesis of aminal quinoxaline and benzoxazine derivatives with good to high yields (up to 99%). These aminal derivatives

  描述了在金属和无光催化剂条件下通过可见光照射加速的环胺（二氢喹喔啉酮和二氢苯并恶嗪酮）与偶氮二羧酸二烷基酯的直接 sp 3 C-H 胺化。该协议具有非常温和的反应条件，用于合成氨基喹喔啉和苯并恶嗪衍生物，产率从好到高（高达 99%）。这些缩醛胺衍生物代表了用于不同合成 quinoxalin-2-one 衍生物的通用构件。
• Application du systeme Me3SiClLiTHF a la synthese d'acylsilanes, d'alcools, d'aldehydes, d'esters et de nitriles C-silicies
  作者：J.-P. Picard、A. Ekouya、J. Dunogues、N. Duffaut、R. Calas

  DOI：10.1016/s0022-328x(00)94144-5

  日期：1975.7

  Synthesis of C-silylated products by silylation of various functional saturated derivatives (aldehydes, nitriles, acid anhydrides and esters), by mens of the Me3SiClLiTHF system used at 0–10°C, is described. Most of the products obtained are new. A mechanism explaining the formation of these derivatives is proposed.

  描述了通过在0–10°C下使用Me 3 SiCl 3 Li 3 THF体系对各种功能性饱和衍生物（醛，腈，酸酐和酯）进行甲硅烷基化来合成C-硅烷化产物的方法。获得的大多数产品都是新产品。提出了解释这些衍生物形成的机理。
• YAMAMOTO, YOSHINORI;MARUYAMA, KAZUHIRO;MATSUMOTO, KIYOSHI, ORGANOMETALLICS, 1984, 3, N 10, 1583-1585
  作者：YAMAMOTO, YOSHINORI、MARUYAMA, KAZUHIRO、MATSUMOTO, KIYOSHI

  DOI：——

  日期：——
• Halogen-Bond-Catalyzed Addition of Carbon-Based Nucleophiles to <i>N</i>-Acylimminium Ions
  作者：Yuk-Cheung Chan、Ying-Yeung Yeung

  DOI：10.1021/acs.orglett.9b02006

  日期：2019.7.19

  N-acylimminium ions are an important class of synthetic intermediates to produce diverse products upon treatment with different nucleophiles. Most of the reported catalytic protocol involved moisture-sensitive Lewis acids or transition metal. Herein, we reported an organocatalytic version by using halogen-bond catalyst as mild Lewis acid through anion-abstraction strategy. A preliminary result of enantioselective version by employing a chiral BINOL-phosphate anion has also been demonstrated.