2-bromo-3,5-dimethoxystyrene | 224629-50-9

• 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-bromo-3,5-dimethoxystyrene
• 英文别名: 2-Bromo-1-ethenyl-3,5-dimethoxybenzene
• CAS: 224629-50-9
• 化学式: C₁₀H₁₁BrO₂
• 分子量: 243.1
• InChiKey: WUDYFYWXDRAWOM-UHFFFAOYSA-N

物化性质

• 沸点：
  307.4±37.0 °C(predicted)
• 密度：
  1.353±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 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-bromo-3,5-dimethoxystyrene 在 potassium osmate(VI) dihydrate 、 potassium carbonate 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 21.0h， 生成 (R)-3-(hydroxymethyl)-5,7-dimethoxyisobenzofuran-1(3H)-one
  参考文献：
  名称：

  氰基肉桂酸酯和苯乙烯衍生物的CN辅助氧化环化：轻松进入3取代的手性邻苯二甲酸盐†

  摘要：

  邻氰基肉桂酸酯和苯乙烯衍生物的不对称二羟基化（AD）导致高光学纯度的手性邻苯二甲酸酯骨架的有效构建。这种独特的反应的特征在于CN和渗透酸基团之间异常的协同作用，从而导致AD过程的速率提高。天然产物的合成和结构/立体化学分配充分证明了该方法。

  DOI：

  10.1039/c2ob25409c
• 作为产物：
  描述：

  3,5-二甲氧基苯甲醛 在 溴 作用下， 以 四氢呋喃 、 溶剂黄146 为溶剂， 反应 16.83h， 生成 2-bromo-3,5-dimethoxystyrene
  参考文献：
  名称：

  闭环复分解法合成3,4-苯并四氢呋喃酮

  摘要：

  将邻甲硅烷基化的苯乙烯或邻甲硅烷基化的苯甲醛二甲基乙缩醛添加到2,2-二甲氧基戊-4-烯醛7中。所得的醇被带到芳族二烯酮10上。这些通过烯烃复分解而闭环。二甲基缩酮部分的水解和烯醇化提供了3,4-苯并tropolones 5。总的来说，这种访问包括4–6个步骤，总计22–81％的收益。

  DOI：

  10.1021/ol400510j

文献信息

• Syntheses of 3,4-Benzotropolones by Ring-Closing Metatheses
  作者：Deniz Arican、Reinhard Brückner

  DOI：10.1021/ol400510j

  日期：2013.6.7

  Ortho-lithiated styrenes or ortho-lithiated benzaldehyde dimethyl acetals were added to 2,2-dimethoxypent-4-enals 7. The resulting alcohols were carried on to the aromatic dienones 10. These were ring-closed by olefin metathesis. Hydrolysis of the dimethyl ketal moiety and enolization provided the 3,4-benzotropolones 5. Overall, this access comprises 4–6 steps and totaled a 22–81% yield.

  将邻甲硅烷基化的苯乙烯或邻甲硅烷基化的苯甲醛二甲基乙缩醛添加到2,2-二甲氧基戊-4-烯醛7中。所得的醇被带到芳族二烯酮10上。这些通过烯烃复分解而闭环。二甲基缩酮部分的水解和烯醇化提供了3,4-苯并tropolones 5。总的来说，这种访问包括4–6个步骤，总计22–81％的收益。
• Oxygenated Dihydrophenanthrenes Via Quinol Acetals: A Brief Synthesis of Orchinol
  作者：Teresa J. Broering、Gary W. Morrow

  DOI：10.1080/00397919908086083

  日期：1999.4

  The dihydrophenanthrene phytoalexin Orchinol was synthesized in 5 steps from commercially available 3,5-dimethoxybenzaldehyde. The approach utilized a new synthon, p-benzoquinone dibenzylmonoacetal, which served as a phenol 3,4-dication equivalent in an arylation-cyclization sequence.
• Enantioselective Construction of Spiro Quaternary Carbon Stereocenters via Pd-Catalyzed Intramolecular α-Arylation
  作者：Ting Wu、Xuehua Kang、Heng Bai、Wenrui Xiong、Guangqing Xu、Wenjun Tang

  DOI：10.1021/acs.orglett.0c01129

  日期：2020.6.19

  We herein report the development of a sterically hindered and electron-rich P-chiral monophosphorus biaryl ligand that has enabled a general and efficient enantioselective intramolecular alpha-arylation, providing access to a wide series of [4.4], [4.5], and [4.6]-spirocycles with chiral benzylic quaternary carbons in high yields with good to excellent enantioselectivities. A pronounced water effect on enantioselectivity is observed.
• CN-assisted oxidative cyclization of cyano cinnamates and styrene derivatives: a facile entry to 3-substituted chiral phthalides
  作者：R. Santhosh Reddy、I. N. Chaithanya Kiran、Arumugam Sudalai

  DOI：10.1039/c2ob25409c

  日期：——

  of o-cyano cinnamates and styrene derivatives leads to efficient construction of chiral phthalide frameworks in high optical purities. This unique reaction is characterized by unusual synergism between CN and osmate groups resulting in rate enhancement of the AD process. The method is amply demonstrated by the synthesis and the structural/stereochemical assignment of the natural products.

  邻氰基肉桂酸酯和苯乙烯衍生物的不对称二羟基化（AD）导致高光学纯度的手性邻苯二甲酸酯骨架的有效构建。这种独特的反应的特征在于CN和渗透酸基团之间异常的协同作用，从而导致AD过程的速率提高。天然产物的合成和结构/立体化学分配充分证明了该方法。
• Mechanistic Studies of Copper(I)-Catalyzed 1,3-Halogen Migration
  作者：Ryan Van Hoveln、Brandi M. Hudson、Henry B. Wedler、Desiree M. Bates、Gabriel Le Gros、Dean J. Tantillo、Jennifer M. Schomaker

  DOI：10.1021/ja511236d

  日期：2015.4.29

  An ongoing challenge in modern catalysis is to identify and understand new modes of reactivity promoted by earth-abundant and inexpensive first-row transition metals. Herein, we report a mechanistic study of an unusual copper(I)-catalyzed 1,3-migration of 2-bromostyrenes that reincorporates the bromine activating group into the final product with concomitant borylation of the aryl halide bond. A combination of experimental and computational studies indicated this reaction does not involve any oxidation state changes at copper; rather, migration occurs through a series of formal sigmatropic shifts. Insight provided from these studies will be used to expand the utility of aryl copper species in synthesis and develop new ligands for enantioselective copper-catalyzed halogenation.