2-(4-Methoxyphenyl)-2-(trimethylsilyl)-1,3-dithiane | 132274-45-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-(4-Methoxyphenyl)-2-(trimethylsilyl)-1,3-dithiane
• 英文别名: 2-(4-methoxyphenyl)-2-trimethylsilyl-1,3-dithiane；[2-(4-Methoxyphenyl)-1,3-dithian-2-yl]-trimethylsilane
• CAS: 132274-45-4
• 化学式: C₁₄H₂₂OS₂Si
• 分子量: 298.546
• InChiKey: NHNSRKSKTSYRSR-UHFFFAOYSA-N

物化性质

• 沸点：
  388.2±42.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  59.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(4-Methoxyphenyl)-2-(trimethylsilyl)-1,3-dithiane 在 copper(II) oxide 、 copper dichloride 作用下， 以 正己烷 、 丙酮 为溶剂， 反应 3.5h， 生成 4-甲氧基二苯甲酮
  参考文献：
  名称：

  Photochemically Promoted Transition Metal-Free Cross-Coupling of Acylsilanes with Organoboronic Esters

  摘要：

  Intermolecular carbon-carbon bond formation between acylsilanes and organoboronic esters was achieved by photoirradiation under almost neutral, transition metal-free conditions. In this reaction, siloxycarbenes generated by photoisomerization of acylsilanes reacted with boronic esters to give the formal B-C bond insertion intermediates, which underwent unique rearrangement to afford the cyclic alpha-alkoxyboronic esters. Acidic treatment of the resulting crude products under air furnished the cross-coupled ketones in good yields.

  DOI：

  10.1021/ja1102597
• 作为产物：
  描述：

  4-甲氧基苯基-1,3-二噻戊环 在 正丁基锂 、 copper(II) sulfate 、 对苯醌 、 sodium iodide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 25.0h， 生成 2-(4-Methoxyphenyl)-2-(trimethylsilyl)-1,3-dithiane
  参考文献：
  名称：

  Facile deprotection of dithioacetals by using a novel 1,4-benzoquinone/cat. NaI system

  摘要：

  The combination of 1,4-benzoquinone and a catalytic amount of NaI was found to be effective for the deprotection of dithioacetals. The reactions proceeded efficiently under mild, near-neutral reaction conditions, producing a wide range of aryl and alkyl aldehydes and ketones generally in high yields with good functional group compatibility. The method developed therefore represents a general, facile, and highly applicable approach for deprotecting dithioacetals. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.08.061

文献信息

• Oxidative [1,2]-Brook Rearrangements Exploiting Single-Electron Transfer: Photoredox-Catalyzed Alkylations and Arylations
  作者：Yifan Deng、Qi Liu、Amos B. Smith

  DOI：10.1021/jacs.7b05165

  日期：2017.7.19

  Oxidative [1,2]-Brook rearrangements via hypervalent silicon intermediates induced by photoredox-catalyzed single-electron transfer have been achieved, permitting the formation of reactive radical species that can engage in alkylations and arylations.

  已经实现了通过光氧化还原催化的单电子转移诱导的高价硅中间体的氧化 [1,2]-布鲁克重排，允许形成可以参与烷基化和芳基化的反应性自由基物种。
• Enantioselective synthesis of α-hydroxysilanes by bioreduction of aroyltrimethylsilanes
  作者：Amauri F. Patrocínio、Ivan R. Corrêa Jr、Paulo J. S. Moran

  DOI：10.1039/a906335h

  日期：——

  Aromatic acylsilanes [Ar-CO-SiMe3; Ar = C6H5, 4-ClC6H4, 2-, 3- and 4-OMeC6H4, 3,4-(OMe)2C6H3 and 3,4-OCH2OC6H3] were reduced by baker’s yeast to optically active α-silyl alcohols in 20–70% yield and 43–88% ee. Comments are made on the influence of silicon in this bioreduction reaction.

  芳香基乙酰硅烷 [Ar-CO-SiMe3; Ar = C6H5, 4-ClC6H4, 2-, 3- 和 4-OMeC6H4, 3,4-(OMe)2C6H3 和 3,4-OCH2OC6H3] 通过面包酵母还原为光学活性的α-硅基醇，产率为20-70％，对映体过量为43-88％。对硅在这类生物还原反应中的影响进行了评论。
• Palladium-Catalyzed Fluoride-Free Cross-Coupling of Intramolecularly Activated Alkenylsilanes and Alkenylgermanes: Synthesis of Tamoxifen as a Synthetic Application
  作者：Kenji Matsumoto、Mitsuru Shindo

  DOI：10.1002/adsc.201100627

  日期：2012.3

  intramolecular hypercoordination of a carboxylic acid is a powerful activation strategy for the palladium‐catalyzed cross‐coupling reaction of trialkyl(vinyl)silanes and trialkyl(vinyl)germanes under fluoride‐free conditions. Z‐β‐Trialkylsilyl‐ and Z‐β‐trialkylgermylacrylic acids, synthesized stereoselectively by olefination with ynolates, are highly stable and useful reagents for cross‐coupling with a variety

  我们已经证明，在无氟条件下，羧酸的分子内高配位是钯催化的三烷基（乙烯基）硅烷与三烷基（乙烯基）锗烷的交叉偶联反应的强大活化策略。Z -β-三烷基甲硅烷基和Z -β-三烷基锗烷基丙烯酸是通过烯醇酸酯与烯烃的立体选择性合成而来的，是高度稳定且有用的试剂，可与多种芳基碘化物交叉偶联，从而提供具有立体控制和多样性的，具有不同碳取代基的四取代烯烃导向的方式。还报道了立体选择性合成（Z）-他莫昔芬的应用。
• Synthesis, Structure, and Photochemistry of 2-Silyl- and 2-Disilanyl-2-aryl-1,3-dithiane Derivatives
  作者：Anugula Mahipal Reddy、Shinobu Tsutsui、Kenkichi Sakamoto

  DOI：10.1246/cl.2001.476

  日期：2001.5

  A series of 2-silyl- and 2-disilanyl-substituted 2-aryl-1,3-dithiane derivatives were prepared by the reactions of 2-aryl-2-lithio-1,3-dithianes with the corresponding chlorosilanes. Photolysis of 2-phenyl-2-(pentamethyldisilanyl)-1,3-dithiane resulted in the intermediary formation of 1,1-dimethyl-2-phenyl-2-(trimethylsilyl)-1-silaethene.

  通过 2-芳基-2-硫代-1,3-二噻烷与相应的氯硅烷反应，制备了一系列 2-硅烷基和 2-二硅烷基取代的 2-芳基-1,3-二噻烷衍生物。2- 苯基-2-(五甲基二硅烷基)-1,3-二噻烷的光解会产生 1,1-二甲基-2-苯基-2-(三甲基硅烷基)-1-硅烷的中间产物。
• Visible-Light-Induced Siloxycarbene Addition to N═N of Azodicarboxylates: Synthesis of Acyl Hydrazides from Acylsilanes
  作者：Mohammad Saleem、Akash Ratwan、Pokhriyal Yamini、Dongari Yadagiri

  DOI：10.1021/acs.orglett.4c00185

  日期：2024.3.15

  We report the synthesis of acyl hydrazides from acylsilanes in the presence of visible light without the aid of additives or transition metals. Acylsilanes underwent [1,2]-Brook rearrangement to generate the nucleophilic siloxycarbenes which on further addition to N═N of azodicarboxylates produced the acyl hydrazides. Control experiments indicate that the reaction proceeds through the singlet carbene

  我们报道了在可见光存在下，无需添加剂或过渡金属的帮助，由酰基硅烷合成酰肼。酰基硅烷经历[1,2]-布鲁克重排生成亲核硅氧碳烯，其进一步加成到偶氮二甲酸酯的N=N上产生酰肼。对照实验表明反应通过单线态卡宾中间体进行。酰肼官能团向其他官能团的转化得到了证明，包括候选药物吗氯贝胺的合成。