2- methoxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol | 1437769-82-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 2- methoxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol
• 英文别名: 2-Methoxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-YL)phenol；2-methoxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol
• CAS: 1437769-82-8
• 化学式: C₁₃H₁₉BO₄
• 分子量: 250.102
• InChiKey: IRKDHCQUMBNYFG-UHFFFAOYSA-N

物化性质

• 沸点：
  355.1±32.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

安全信息

• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335

反应信息

• 作为反应物：
  描述：

  2- methoxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol 在 1,1'-双(二苯膦基)二茂铁二氯化钯(II)二氯甲烷复合物 、 偶氮二甲酸二异丙酯 、 三乙基硼氢化锂 、 三乙胺 、 三苯基膦 、 N,N'-羰基二咪唑 、 三氟乙酸 、 N-(2,2,6,6-tetramethyl-1-oxopiperidin-1-ium-4-yl)acetamide tetrafluoroborate 作用下， 以 四氢呋喃 、 水 、 甲苯 、 乙腈 为溶剂， 反应 95.5h， 生成 (4aR,5R,6S,8aS)-5,6-dihydroxy-3-methoxy-11-methyl-4a,5,11,12-tetrahydro-6H-benzo[2,3]benzofuro[4,3-cd]azepin-10(9H)-one
  参考文献：
  名称：

  （-）-和（+）-加兰他敏某些衍生物和类似物的合成及其抑制乙酰胆碱酯酶能力的评估

  摘要：

  （-）-和（+）-对映体形式的某些双加氧和单加氧衍生物（例如分别为2和3）和类似物（例如4，D环的2的单环类似物）的合成报告了生物碱加兰他敏[（-）- 1 ]的含量。已经评估了它们全部抑制乙酰胆碱酯酶的能力，但是与对接研究的预测相反，没有一个与该酶强烈结合。

  DOI：

  10.1021/acs.joc.7b01062
• 作为产物：
  描述：

  木榴油 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 1,3,5-三甲氧基苯 、 4,4'-二叔丁基-2,2'-二吡啶 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 21.33h， 生成 2- methoxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol
  参考文献：
  名称：

  多取代苯炔由酚合成多取代苯

  摘要：

  介绍了一种从简单酚类到芳烃中间体合成多功能芳烃的新方法。多取代的芳烃前体通过 Ir 催化的 C-H 硼基化、脱硼硫基化、O-三氟甲磺酸化、S-氧化以及通过亚砜部分指导的邻位去质子化进一步改性由苯酚制备。通过转化由邻亚磺酰基芳基三氟甲磺酸酯产生的高度官能化的芳烃中间体，合成了各种多取代芳烃。

  DOI：

  10.1055/a-1834-2927

文献信息

• Ligand-Induced Regioselectivity in Metal-Catalyzed Aryne Reactions Using Borylaryl Triflates as Aryne Precursors
  作者：Brylon N. Denman、Erin E. Plasek、Courtney C. Roberts

  DOI：10.1021/acs.organomet.3c00103

  日期：2023.5.22

  The utility of reactions using unsymmetrically substituted aryne intermediates can be negatively impacted by issues with regioselectivity as these reactions are substrate controlled. This leaves no avenues for improving regioselectivity without altering the substrate which has led to numerous reports about how to enhance or reverse this regioselectivity in metal-free aryne reactions by changing the

  使用不对称取代的芳烃中间体的反应效用可能会受到区域选择性问题的负面影响，因为这些反应是底物控制的。这就没有途径可以在不改变底物的情况下提高区域选择性，这导致了大量关于如何通过改变电子元件来增强或逆转无金属芳烃反应中的区域选择性的报道。对于具有金属结合芳烃中间体的系统，不存在此类研究，这些系统通常具有较差的区域选择性。在此，我们报道了一种通过催化剂控制在金属催化的芳烃二官能团化中实现区域选择性的方法。通过使用不对称的配体环境，可以诱导选择性（高达 9：91 r.r.）。这些研究表明，催化剂设计会影响金属催化芳烃反应的选择性。
• Generation of Arynes via Ate Complexes of Arylboronic Esters with an <i>ortho</i>-Leaving Group
  作者：Yuto Sumida、Tomoe Kato、Takamitsu Hosoya

  DOI：10.1021/ol401140d

  日期：2013.6.7

  An efficient method of generating aryne has been achieved by treating ortho-(trifluoromethanesulfonyloxy)arylboronic acid pinacol ester with tert-or sec-butyllithium. Monitoring the reaction by B-11 NMR has indicated that a boron-ate complex formed in situ is the eventual precursor that converts into aryne near room temperature. The prior formation of the ate complex at a low temperature has enabled us to use various arynophiles, including those bearing base-sensitive groups. The ready availability of the aryne precursors and mutual orthogonality in aryne generation with widely used ortho-silylaryl triflate have enhanced the utility of the method.
• Ir-Catalyzed ortho-Borylation of Phenols Directed by Substrate–Ligand Electrostatic Interactions: A Combined Experimental/in Silico Strategy for Optimizing Weak Interactions
  作者：Buddhadeb Chattopadhyay、Jonathan E. Dannatt、Ivonne L. Andujar-De Sanctis、Kristin A. Gore、Robert E. Maleczka、Daniel A. Singleton、Milton R. Smith

  DOI：10.1021/jacs.7b02232

  日期：2017.6.14

  A strategy for affecting ortho-versus meta/para selectivity in Ir-catalyzed C-H borylations (CHBs) of phenols is described. From selectivity observations with ArylOBpin (pin-7 pinacolate), it is hypothesized that an electrostatic interaction between the partial negatively,charged OBpin group and the partial positively charged bipyridine ligand of the catalyst favors ortho selectivity. Experimental and computational studies designed to test this hypothesis support it. From further computational work a second generation, in silico designed catalyst emerged; where replacing Bpin with Beg (eg, = ethylene glycolate) was predicted to significantly improve ortho selectivity. Experinientally, reactions employing B(2)eg(2) gave ortho selectivities > 99%. Adding triethylamine significantly improved conversions. This ligand-substrate electrostatic interaction provides a unique control element for selective C-H functionalization.
• The Synthesis of Certain Derivatives and Analogues of (−)- and (+)-Galanthamine and an Assessment of their Capacities to Inhibit Acetylcholine Esterase
  作者：Joshua N. Buckler、Ehab S. Taher、Nicolas J. Fraser、Anthony C. Willis、Paul D. Carr、Colin J. Jackson、Martin G. Banwell

  DOI：10.1021/acs.joc.7b01062

  日期：2017.8.4

  Syntheses of certain di- and mono-oxygenated derivatives (e.g., 2 and 3, respectively) and analogues (e.g., 4, a D-ring monoseco-analogue of 2) of both the (−)- and (+)-enantiomeric forms of the alkaloid galanthamine [(−)-1] are reported. All have been assessed for their capacities to inhibit acetylcholine esterase but, in contrast to the predictions from docking studies, none bind strongly to this

  （-）-和（+）-对映体形式的某些双加氧和单加氧衍生物（例如分别为2和3）和类似物（例如4，D环的2的单环类似物）的合成报告了生物碱加兰他敏[（-）- 1 ]的含量。已经评估了它们全部抑制乙酰胆碱酯酶的能力，但是与对接研究的预测相反，没有一个与该酶强烈结合。
• Synthesis of Multisubstituted Benzenes from Phenols via Multisubstituted Benzynes
  作者：Suguru Yoshida、Akira Nagai、Akihiro Kobayashi、Yuki Sakata、Yasunori Minami、Keisuke Uchida、Takamitsu Hosoya

  DOI：10.1055/a-1834-2927

  日期：2022.11

  synthesize multifunctionalized arenes from simple phenols through aryne intermediates is described. Multisubstituted aryne precursors were prepared from phenols by Ir-catalyzed C–H borylation, deborylthiolation, O-triflylation, S-oxidation, and further modification through ortho-deprotonation directed by the sulfoxide moiety. Various multisubstituted arenes were synthesized by transformations of highly

  介绍了一种从简单酚类到芳烃中间体合成多功能芳烃的新方法。多取代的芳烃前体通过 Ir 催化的 C-H 硼基化、脱硼硫基化、O-三氟甲磺酸化、S-氧化以及通过亚砜部分指导的邻位去质子化进一步改性由苯酚制备。通过转化由邻亚磺酰基芳基三氟甲磺酸酯产生的高度官能化的芳烃中间体，合成了各种多取代芳烃。