4,5-dimethyl-2-(4-methoxyphenyl)-1,3,2-dioxaborolane | 215877-38-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4,5-dimethyl-2-(4-methoxyphenyl)-1,3,2-dioxaborolane
• 英文别名: 2-(4-Methoxyphenyl)-4,5-dimethyl-1,3,2-dioxaborolane
• CAS: 215877-38-6
• 化学式: C₁₁H₁₅BO₃
• 分子量: 206.049
• InChiKey: NIPMLVRBSYDNBO-UHFFFAOYSA-N

物化性质

• 沸点：
  315.6±25.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.21
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl [(E)-1-phenyloct-1-en-3-yl] carbonate 、 4,5-dimethyl-2-(4-methoxyphenyl)-1,3,2-dioxaborolane 在 (1,1'-双(二苯基膦)二茂铁)二氯化镍 、 甲基锂 作用下， 生成 (E)-3-(4-methoxyphenyl)-1-phenyl-1-octene
  参考文献：
  名称：

  Nickel-Catalyzed Coupling Reaction of 1,3-Disubstituted Secondary Allylic Carbonates and Lithium Aryl- and Alkenylborates

  摘要：

  This account describes coupling reaction of 1,3-disubstituted secondary allylic carbonates with lithium aryl- and alkenylborates in the presence of a nickel. catalyst. Berates examined are 4, 5, and 6, and reactivity and selectivity were investigated using the allylic carbonates la and Ib. Coupling of la,b with berates 4 was effected with the nickel catalyst, NiCl2(PPh(3))(2) or NiCl2(dppf), in THF at 45-65 degrees C to provide products 3 in good yields with almost 100% regio- and stereoselectivities. Trivalent organoboranes prepared from acetylenes by hydroboration with catecholborane also underwent coupling reaction with la,b after transformation to berates 5 with MeLi. Though coupling using 4 and 5 required elevated temperature (45-65 degrees C), cyclic berates 6 prepared in situ from boronates 8 and MeLi were found to couple with la,b at room temperature or below. Regio- and stereoselectivities were almost 100% as were observed in the cases of 4 and 5. In these reactions, palladium complexes such as Pd(PPh(3))(4), Pd-2(dba)(3) . CHCl3 + 2 PPh(3) showed no catalytic activity. Stereochemical aspect of the present reaction was studied using cyclohexenyl carbonate 24 with 2-furylborate 4e and phenylborate 6a, and was found to proceed with overall anti fashion. With additional experiments, the mechanism of the present reaction was discussed in terms of transient pi-allylnickel intermediates.

  DOI：

  10.1021/jo960458c
• 作为产物：
  描述：

  4-甲氧基苯硼酸 、 2,3-丁二醇 在 magnesium sulfate 作用下， 以 苯 为溶剂， 生成 4,5-dimethyl-2-(4-methoxyphenyl)-1,3,2-dioxaborolane
  参考文献：
  名称：

  一种将芳基和烯基安装到环戊烯环上并合成前列腺素的新方法。

  摘要：

  为了构建合成环戊烷的新策略，研究了过渡金属催化的顺式4-环戊烯-1,3-二醇单乙酸酯1与硬亲核试剂R（T）-m的偶联反应（图1中的等式1） 。尽管使用PhZnCl，PhSnMe（3），[Ph-B（Me）（OCH（Me）CH（Me）O）]-Li（+）（6a）（源自硼酸酯4a（R（T）= Ph）和MeLi）在钯或镍催化剂的存在下会导致产生未知化合物烯酮16和/或酮17或回收1，新的硼酸盐5a（由4a和n-BuLi衍生）在室温下在THF中存在镍催化剂（NiCl（2）（PPh（3））（2））提供了反式偶合产物2a（R（T）= Ph）和3a（R（T）= Ph）综合产量高，但产品比率低至0.9：1。比例提高到13：通过向反应混合物中加入t-BuCN和NaI，得到1。这是1与硬亲核试剂反应的第一个成功实例，用添加剂实现的比例增加是前所未有的。该试剂系统（硼酸盐5（1.2-1.8当量），NiCl（2）（P

  DOI：

  10.1021/jo020375y

文献信息

• Nickel-catalyzed coupling reaction of lithium organoborates and aryl mesylates possessing an electron withdrawing group
  作者：Yuichi Kobayashi、Ryo Mizojiri

  DOI：10.1016/0040-4039(96)01984-3

  日期：1996.11

  In the presence of NiCl2(PPh3)2 as catalyst, p-methoxycarbonylphenyl mesylate (5) and tosylate (6) react with lithium arylborates 4 (Ar = 2-furyl, Ph, p-Me-Ph; p-Me-Ph) at room temperature to afford the coupling products in high yields. Similarly, mesylates 9–11 coupled with these borates 4 efficiently.

  在作为催化剂的NiCl 2（PPh 3）2存在下，对甲氧基羰基苯基甲磺酸酯（5）和甲苯磺酸酯（6）与芳基硼酸锂4（Ar = 2-呋喃基，Ph，p-Me-Ph; p-Me-在室温下，以高收率获得偶联产物。同样，甲磺酸盐9-11与这些硼酸盐4高效结合。
• Scope and limitation of the nickel-catalyzed coupling reaction between lithium borates and mesylates
  作者：Yuichi Kobayashi、Anthony D. William、Ryo Mizojiri

  DOI：10.1016/s0022-328x(02)01174-9

  日期：2002.7

  Coupling reaction of aryl borates and mesylates derived from phenols and enols was studied. Mesylates with an electron-withdrawing group or ring were highly reactive at room temperature in the presence of NiCl2(PPh3)(2) to furnish the coupling products in good yields. (C) 2002 Elsevier Science B.V. All rights reserved.
• Zinc Borates: Functionalized Hard Nucleophiles for Coupling Reactions with Secondary Allylic Acetates
  作者：Yuichi Kobayashi、Yuko Tokoro、Kengo Watatani

  DOI：10.1002/1099-0690(200012)2000:23<3825::aid-ejoc3825>3.3.co;2-7

  日期：2000.12
• Arylation of 8-Acetoxyoctalenone in a Nickel-Catalyzed Coupling Reaction with Lithium Arylborates
  作者：Yuichi Kobayashi、Michiko Ito

  DOI：10.1002/1099-0690(200010)2000:20<3393::aid-ejoc3393>3.0.co;2-c

  日期：2000.10

  In order to find a suitable organometallic compound and a catalyst for the arylation of 8-acetoxyoctalenone 4 (a stereoisomeric mixture of 4 alpha and 4 beta), phenylation was first-investigated with PhZnX (7: X = Cl; 8: X = Br)/Pd or Ni cat., PhSnBu3 (9)/Pd cat. and LiCl, and [PhB(Bu)(OCHMeCHMeO)]Li (10a)/Ni cat. Berate 10a provided the desired product 11a with high stereoselectivity. The stereochemical outcome was irrespective of the stereochemistry of the acetoxy group in 4. Four more aryl groups, p-R-C6H4 (R = Me, MeO, Ph, and Me2N), were installed stereoselectively with this method.
• Realization of high regioselectivity in the coupling reaction of a cyclopentadiene monoepoxide equivalent and aryl nucleophiles
  作者：Yuichi Kobayashi、Eisuke Takahisa、Shahid B. Usmani

  DOI：10.1016/s0040-4039(97)10654-2

  日期：1998.2

  Coupling reaction of monoacetate 2 and aryl hard nucleophiles is realized for the first time, which consists of the lithium arylborates as hard nucleophiles and NiCl2(PPh3)(2) as a catalyst. More importantly, the independent effects of t-BuCN and NaI and their synergistic function are discovered to increase regioselectivity furnishing trans 1,3-isomers 6 as the major products. (C) 1998 Elsevier Science Ltd. All rights reserved.