2-((tert-butyldimethylsilyl)oxy)-N,N-diethyl-4-methoxybenzamide | 460348-03-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-((tert-butyldimethylsilyl)oxy)-N,N-diethyl-4-methoxybenzamide
• 英文别名: 2-[tert-butyl(dimethyl)silyl]oxy-N,N-diethyl-4-methoxybenzamide
• CAS: 460348-03-2
• 化学式: C₁₈H₃₁NO₃Si
• 分子量: 337.535
• InChiKey: FDXUMDFVLUPZKV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.56
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-((tert-butyldimethylsilyl)oxy)-N,N-diethyl-4-methoxybenzamide 在 sodium hydroxide 、 叔丁基锂 作用下， 以 乙二醇二甲醚 、 乙醚 、 二氯甲烷 、 水 、 正戊烷 为溶剂， 反应 6.17h， 生成 2-Bromo-6-hydroxy-4-methoxybenzoic acid
  参考文献：
  名称：

  Convergent stereospecific synthesis of C292 (or LL-Z1640-2), and hypothemycin. Part 1

  摘要：

  The stereospecific synthesis of the precursors required for the 14-membered ring formation either via an intramolecular Suzuki coupling or via an intermolecular Suzuki coupling followed by a macrolactonisation is herein reported. One-pot Suzuki couplings were here achieved with vinyldisiamylboranes which were generated in situ from the related chiral precursor. The present convergent approach of C292 (or LL-21640-2) and hypothemycin gives a flexible access to related macrolides. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00870-5
• 作为产物：
  描述：

  4-甲氧基水杨酸 在 草酰氯 、 N,N-二异丙基乙胺 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.5h， 生成 2-((tert-butyldimethylsilyl)oxy)-N,N-diethyl-4-methoxybenzamide
  参考文献：
  名称：

  Two remarkable epimerizations imperative for the success of an asymmetric total synthesis of (+)-aigialospirol

  摘要：

  在探索以环缩醛连接的环化复分解反应为特征的对映选择性合成(+)-aigialospirol的过程中，我们发现了两种非凡的消旋化反应。通过建模，我们能够利用这两种意想不到的消旋化反应，确保成功而简洁的全合成，从而将环缩醛连接的RCM牢固确立为天然产物合成中的有力策略。最重要的是，计算使我们能够充分理解这两种消旋化反应的本质和机理，这对全合成工作至关重要。

  DOI：

  10.1007/s11426-010-4176-8

文献信息

• Triflic acid mediated sequential cyclization of ortho-alkynylarylesters with ammonium acetate
  作者：Maciej E. Domaradzki、Xiaochen Liu、Jiye Ong、Gyeongah Yu、Gan Zhang、Ariel Simantov、Eliyahu Perl、Yu Chen

  DOI：10.1016/j.tet.2020.131437

  日期：2020.9

  A triflic acid (TfOH) mediated sequential cyclization of ortho-alkynylarylesters and ammonium acetate (NH4OAc) was reported. The reaction took place via a Brønsted acid-mediated intramolecular cyclization of ortho-alkynylarylesters followed by an ammonium acetate participated substitution reaction, forming isoquinolin-1-ones as the major products. Different from most of the known synthetic methods

  报道了三氟乙酸（TfOH）介导的邻炔基芳基酯和乙酸铵（NH 4 OAc）的顺序环化。该反应通过布朗斯台德酸介导的邻位分子内环化反应进行-炔基芳基酯接着乙酸铵参与取代反应，形成异喹啉-1-酮为主要产物。与大多数已知的异喹啉-1-酮合成方法不同，所报道的反应不需要金属催化剂。在少数情况下，获得了区域异构体–异吲哚啉-1-酮与异喹啉-1-酮。还分离了中间体化合物-异色酮-1-酮和异苯并呋喃-1-酮。相互转化实验表明，在布朗斯台德酸诱导的邻炔基芳基酯分子内环化过程中形成的区域异构体。采用这种新方法，可以以中等收率制备天然产物ruprechstyril。
• An Enantioselective Total Synthesis of (+)-Aigialospirol
  作者：Ruth Figueroa、Richard P. Hsung、Christle C. Guevarra

  DOI：10.1021/ol702195w

  日期：2007.11.1

  A concise and enantioselective total synthesis of (+)-aigialospirol is described here, featuring the first complex natural product synthesis that employs a cyclic ketal-tethered ring-closing metathesis strategy and an unexpected stereoselective epimerization of a benzylic hydroxyl group. The 15-step synthetic sequence illustrates the proof-of-concept that such an approach can be competitive with the classical spiroketal formation in the natural product synthesis.
• Convergent stereospecific synthesis of C292 (or LL-Z1640-2), and hypothemycin. Part 1
  作者：Patrice Sellès、Robert Lett

  DOI：10.1016/s0040-4039(02)00870-5

  日期：2002.5

  The stereospecific synthesis of the precursors required for the 14-membered ring formation either via an intramolecular Suzuki coupling or via an intermolecular Suzuki coupling followed by a macrolactonisation is herein reported. One-pot Suzuki couplings were here achieved with vinyldisiamylboranes which were generated in situ from the related chiral precursor. The present convergent approach of C292 (or LL-21640-2) and hypothemycin gives a flexible access to related macrolides. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Two remarkable epimerizations imperative for the success of an asymmetric total synthesis of (+)-aigialospirol
  作者：Ruth Figueroa、John B. Feltenberger、Christle C. Guevarra、Richard P. Hsung

  DOI：10.1007/s11426-010-4176-8

  日期：2011.1

  Two remarkable epimerization processes were uncovered during our pursuit of an enantioselective synthesis of (+)-aigialospirol featuring a cyclic acetal tethered ring-closing metathesis. Through modeling, we were able to turn these two unexpected epimerizations to our advantage via modeling to ensure a successful and concise total synthesis, thereby firmly establishing cyclic acetal tethered RCM as a powerful strategy in natural product synthesis. Most importantly, calculations allowed us to fully understand the nature and the mechanistic course of these two epimerizations that were imperative to the total synthesis efforts.

  在探索以环缩醛连接的环化复分解反应为特征的对映选择性合成(+)-aigialospirol的过程中，我们发现了两种非凡的消旋化反应。通过建模，我们能够利用这两种意想不到的消旋化反应，确保成功而简洁的全合成，从而将环缩醛连接的RCM牢固确立为天然产物合成中的有力策略。最重要的是，计算使我们能够充分理解这两种消旋化反应的本质和机理，这对全合成工作至关重要。