2-methoxy-4-methylphenyl tert-butyldimethylsilyl ether | 153864-82-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-methoxy-4-methylphenyl tert-butyldimethylsilyl ether
• 英文别名: 4-(tert-Butyldimethylsiloxy)-3-methoxytoluene；Tert-butyl-(2-methoxy-4-methylphenoxy)-dimethylsilane
• CAS: 153864-82-5
• 化学式: C₁₄H₂₄O₂Si
• 分子量: 252.429
• InChiKey: PYJHGLZUNQCGJE-UHFFFAOYSA-N

物化性质

• 沸点：
  294.5±28.0 °C(predicted)
• 密度：
  0.927±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.39
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-methoxy-4-methylphenyl tert-butyldimethylsilyl ether 在 N-溴代丁二酰亚胺(NBS) 、 过氧化氢苯甲酰 作用下， 以 四氯化碳 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 生成 {(Z)-3-tert-Butoxycarbonyl-4-[4-(tert-butyl-dimethyl-silanyloxy)-3-methoxy-phenyl]-2-ethoxy-but-1-enyl}-triphenyl-phosphonium; bromide
  参考文献：
  名称：

  Allylidenetriphenylphosphorane as a bifunctional reagent: synthesis of cyclopentenones and .alpha.,.beta.-unsaturated ketones with [3-(alkoxycarbonyl)-2-ethoxy-2-propenylidene]triphenylphosphorane

  摘要：

  When (3-(ethoxycarbonyl)-2-ethoxy-2-propenylidene) triphenylphosphorane (6) was allowed to react with cu-bromo ketones 8a-d in dichloromethane in the presence of Cs2CO3 at room temperature, a [3 + 2] annulation occurred and led to the formation of the corresponding 2-ethoxycyclopentadienes 9a-d in excellent yields. Similarly, bromo thioester 8g underwent the annulation to give 4-(ethylthio)-cyclopentadiene 9g. Secondary bromides 2-bromo-3-pentanone and 2-bromocyclohexanone also afforded tetrasubstituted cyclopentadienes 9e and 9f in moderate yields when 2 equiv of 6 was used. The annulation is believed to proceed through a sequence involving a stepwise alkylation at the gamma position of 6 and an intramolecular Wittig reaction because of the fact that intermediate 11 was isolated. The resulting 2-ethoxycyclopentadienes 9a-g were converted quantitatively into the corresponding cyclopentenones 10a-g upon mild acid treatment. Furthermore, allylidenetriphenylphosphorane underwent a carbon elongation at both ends of the three-carbon unit via an alkylation-Wittig reaction sequence. (3-(tert-Butoxycarbonyl)-2-ethoxy-2-propenylidene)triphenylphosphorane (7) reacted first with alkyl halides and then with aldehydes in the presence of Cs2CO3 to give enol ethers 23a-f, which were converted into alpha,beta-unsaturated ketones 20, 21, and 25c-f by hydrolysis of the enol ether and then decarboxylation. In this way, shogaol (29), the pungent principle component of ginger, was conveniently synthesized starting from 2-methoxy-4-methylphenol.

  DOI：

  10.1021/jo00080a019
• 作为产物：
  描述：

  2-甲氧基-4-甲基苯酚 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 2-methoxy-4-methylphenyl tert-butyldimethylsilyl ether
  参考文献：
  名称：

  Synthesis of α,β-Unsaturated Ketones Using Allylidenetriphenylphosphorane as a Three-carbon Unit

  摘要：

  在碱存在下，3-烷氧羰基-2-乙氧基-2-亚丙烯基三苯基膦通过一锅程序依次与烷基卤化物和醛发生反应，生成中等至高产率的共轭烯醇醚。共轭烯醇醚的水解和随后的脱羧反应提供了一种获得 α、β-不饱和酮的新途径。

  DOI：

  10.1246/cl.1992.2253

文献信息

• P(<i>i</i>-BuNCH₂CH₂)₃N:  An Efficient Promoter for the Nucleophilic Aromatic Substitution Reaction of Aryl Fluorides with Aryl TBDMS (or TMS) Ethers
  作者：Sameer Urgaonkar、John G. Verkade

  DOI：10.1021/ol051108s

  日期：2005.7.1

  [reaction: see text]. The nucleophilic aromatic substitution reaction between electron-deficient aryl fluorides and aryl TBDMS (or TMS) ethers has been shown to be efficiently promoted by proazaphosphatranes such as P(i-BuNCH(2)CH(2))(3)N (3). Excellent yields of diaryl ether products were obtained under unusually mild conditions.

  [反应：请参见文字]。缺电子的芳基氟化物和芳基TBDMS（或TMS）醚之间的亲核芳族取代反应已显示出可以通过原七磷烷（例如P（i-BuNCH（2）CH（2））（3）N（3）有效地促进。在异常温和的条件下，可获得优异的二芳基醚产品收率。
• Enantioselective Synthesis of Imperanene, a Platelet Aggregation Inhibitor
  作者：James C. Shattuck、Cheney M. Shreve、Sandra E. Solomon

  DOI：10.1021/ol0164482

  日期：2001.9.1

  Both enantiomers of imperanene, a platelet aggregation inhibitor, have been synthesized in 82-90% ee. The key step of establishing the chiral center was achieved through stereoselective alkylation with benzyl chloromethyl ether using Enders' RAMP/SAMP chiral auxiliary method. The natural product was determined to be the (S)-enantiomer through comparison of optical rotation data. Reaction: see text

  戊二烯（一种血小板聚集抑制剂）的两种对映体均以82-90％ee的比例合成。建立手性中心的关键步骤是通过使用Enders的RAMP / SAMP手性辅助方法与苄基氯甲基醚进行立体选择性烷基化来实现的。通过旋光度数据的比较确定天然产物为（S）-对映体。反应：见文字。
• Intermolecular C–H activation at benzylic positions: synthesis of (+)-imperanene and (−)-α-conidendrin
  作者：Huw M.L. Davies、Qihui Jin

  DOI：10.1016/s0957-4166(03)00154-x

  日期：2003.4

  An efficient C-H activation of primary benzylic positions by means of rhodium carbenoid induced C-H insertions is described. This key step was used in concise syntheses of (+)-imperanene and (-)-alpha-conidendrin. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Allylidenetriphenylphosphorane as a bifunctional reagent: synthesis of cyclopentenones and .alpha.,.beta.-unsaturated ketones with [3-(alkoxycarbonyl)-2-ethoxy-2-propenylidene]triphenylphosphorane
  作者：Minoru Hatanaka、Yuichiro Himeda、Ritsuo Imashiro、Yasuhiro Tanaka、Ikuo Ueda

  DOI：10.1021/jo00080a019

  日期：1994.1

  When (3-(ethoxycarbonyl)-2-ethoxy-2-propenylidene) triphenylphosphorane (6) was allowed to react with cu-bromo ketones 8a-d in dichloromethane in the presence of Cs2CO3 at room temperature, a [3 + 2] annulation occurred and led to the formation of the corresponding 2-ethoxycyclopentadienes 9a-d in excellent yields. Similarly, bromo thioester 8g underwent the annulation to give 4-(ethylthio)-cyclopentadiene 9g. Secondary bromides 2-bromo-3-pentanone and 2-bromocyclohexanone also afforded tetrasubstituted cyclopentadienes 9e and 9f in moderate yields when 2 equiv of 6 was used. The annulation is believed to proceed through a sequence involving a stepwise alkylation at the gamma position of 6 and an intramolecular Wittig reaction because of the fact that intermediate 11 was isolated. The resulting 2-ethoxycyclopentadienes 9a-g were converted quantitatively into the corresponding cyclopentenones 10a-g upon mild acid treatment. Furthermore, allylidenetriphenylphosphorane underwent a carbon elongation at both ends of the three-carbon unit via an alkylation-Wittig reaction sequence. (3-(tert-Butoxycarbonyl)-2-ethoxy-2-propenylidene)triphenylphosphorane (7) reacted first with alkyl halides and then with aldehydes in the presence of Cs2CO3 to give enol ethers 23a-f, which were converted into alpha,beta-unsaturated ketones 20, 21, and 25c-f by hydrolysis of the enol ether and then decarboxylation. In this way, shogaol (29), the pungent principle component of ginger, was conveniently synthesized starting from 2-methoxy-4-methylphenol.
• Synthesis of α,β-Unsaturated Ketones Using Allylidenetriphenylphosphorane as a Three-carbon Unit
  作者：Minoru Hatanaka、Ritsuo Imashiro、Ikuo Ueda

  DOI：10.1246/cl.1992.2253

  日期：1992.11

  3-Alkoxycarbonyl-2-ethoxy-2-propenylidenetriphenylphosphorane reacts in turn with alkyl halides and aldehydes in the presence of base via a one-pot procedure to give moderate to good yields of conjugated enol ethers. Hydrolysis of the conjugated enol ethers and subsequent decarboxylation provide a novel route to α,β-unsaturated ketones.

  在碱存在下，3-烷氧羰基-2-乙氧基-2-亚丙烯基三苯基膦通过一锅程序依次与烷基卤化物和醛发生反应，生成中等至高产率的共轭烯醇醚。共轭烯醇醚的水解和随后的脱羧反应提供了一种获得 α、β-不饱和酮的新途径。