(E)-methyl-3-phenyl-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)acrylate | 666749-25-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-methyl-3-phenyl-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)acrylate
• 英文别名: (E)-methyl 3-phenyl-2-[(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methl]acrylate；3-phenyl-2-methoxycarbonyl allylboronate；methyl (E)-3-phenyl-2-[(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl]prop-2-enoate
• CAS: 666749-25-3
• 化学式: C₁₇H₂₃BO₄
• 分子量: 302.178
• InChiKey: RHBCWRIIPPVAQE-SDNWHVSQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.34
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  五氟苯甲醛 、 (E)-methyl-3-phenyl-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)acrylate 在 In(OSO₂CF₃)3 作用下， 以 甲苯 为溶剂， 反应 18.0h， 以95%的产率得到
  参考文献：
  名称：

  立体化学的控制：Z-巴豆基硼化后，顺式或反式，反式，γ-二取代-γ-丁内酯的一般合成。

  摘要：

  [反应; 见文]为顺式或反式-β-的高度非对映制备的一般和实用程序，则报告crotylboration或内酯化过程中的γ-二取代-γ丁内酯由路易斯或布朗斯台德酸催化剂的合适的选择。Z-巴豆基硼化产物的顺式立体化学可以在内酯化过程中用强酸逆转。已经提出了碳正离子化机理和催化循环。

  DOI：

  10.1021/ol061566g
• 作为产物：
  描述：

  苯甲醛 在 吡啶 、 potassium acetate 、 二异丁基氢化铝 、 N-甲基吗啉氧化物 、 copper(l) chloride 、 lithium chloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 (E)-methyl-3-phenyl-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)acrylate
  参考文献：
  名称：

  Syntheses of β- and γ-fluorophenyl cis- and trans-α-methylene-γ-butyrolactones

  摘要：

  Preparation of a series of cis-gamma-fluorophenyl-beta-phenyl-alpha-methylene-gamma-butyrolactones is reported via 'allylboration' of fluorobenzaldehydes with (E)-methyl 3-phenyl-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)acrylate. The corresponding trans-gamma-fluorophenyl lactones were prepared either (i) via 'allylboration' using the (Z)-reagents or (ii) via an indium triflate-mediated isomerization of the cis-products. The difficulty in isomerizing difluorinated cis-products confirms the probable intermediacy of carbocations. Finally, the synthesis of cis-beta-fluorophenyl-gamma-phenyl-alpha-methylene-gamma-butyrolactones was achieved via an indium-catalyzed allylation-lactonization of aldehydes with (Z)-2-(bromomethyl)-3-(fluorophenyl)acrylates. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.07.106

文献信息

• Direct Synthesis of Functionalized Allylic Boronic Esters from Allylic Alcohols and Inexpensive Reagents and Catalysts
  作者：Kálmán Szabó、Varinder Aggarwal、Guillaume Dutheuil、Nicklas Selander

  DOI：10.1055/s-2008-1067144

  日期：2008.7

  A remarkably simple and effective system for the direct conversion of allylic alcohols into high value allylic boronic esters using commercially available reagents and catalysts is described.

  描述了一种使用市售试剂和催化剂将烯丙醇直接转化为高价值烯丙硼酸酯的非常简单有效的系统。
• Novel Functionalized Trisubstituted Allylboronates via Hosomi−Miyaura Borylation of Functionalized Allyl Acetates
  作者：P. Veeraraghavan Ramachandran、Debarshi Pratihar、Debanjan Biswas、Amit Srivastava、M. Venkat Ram Reddy

  DOI：10.1021/ol035952z

  日期：2004.2.1

  A series of novel functionalized achiral and chiral allylboronates have been synthesized via the nucleophilic addition of boronates on allyl acetates derived via vinylalumination or Baylis-Hillman reaction of aldehydes. These reagents, upon allylboration with aldehydes, furnish,beta-substituted-alpha-methylene-gamma-butyrolactones stereoselectively.
• Acidity-Directed Synthesis of Substituted γ-Butyrolactones from Aliphatic Aldehydes
  作者：P. Veeraraghavan Ramachandran、Debarshi Pratihar

  DOI：10.1021/ol0705806

  日期：2007.5.1

  The strength of the Lewis or Bronsted acids controls the formation of either beta,gamma-disubstituted-alpha-methylene-gamma-butyrolactones or gamma-substituted-alpha-alkylidene-gamma-butyrolactones via the lactonization or oxonia cope rearrangement-lactonization, respectively, of the borate intermediates resulting from the crotylboration of aliphatic aldehydes with ester-containing crotylboronates, such as (E)-methyl 2-boramethyl-2-butenoates.
• WO2007/81966
  申请人：——

  公开号：——

  公开（公告）日：——
• Pd-Catalyzed Cross-Coupling of Baylis−Hillman Acetate Adducts with Bis(pinacolato)diboron:  An Efficient Route to Functionalized Allyl Borates
  作者：George W. Kabalka、Bollu Venkataiah、Gang Dong

  DOI：10.1021/jo0492618

  日期：2004.8.1

  The cross-coupling of Baylis-Hillman acetate adducts and bis(pinacolato)diboron proceeds readily in high yields in the presence of palladium catalyst to produce 3-substituted-2-alkoxycarbonyl allylboronates. These allylboronates can be transformed to stable allyl trifluoroborate salts by addition of excess aqueous KHF2. Both the allylboronate and allyltrifluoroborate derivatives react with aldehydes to afford functionalized homoallylic alcohols stereo-selectively.