4,4,5,5-tetramethyl-2-(2-((methylthio)methyl)phenyl)-1,3,2-dioxaborolane

• 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: 4,4,5,5-tetramethyl-2-(2-((methylthio)methyl)phenyl)-1,3,2-dioxaborolane
• 英文别名: 4,4,5,5-tetramethyl-2-[2-(methylsulfanylmethyl)phenyl]-1,3,2-dioxaborolane
• 化学式: C₁₄H₂₁BO₂S
• 分子量: 264.197
• InChiKey: WCPVYKGJWCQNPT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.85
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  43.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-溴-5-硝基吡啶 、 4,4,5,5-tetramethyl-2-(2-((methylthio)methyl)phenyl)-1,3,2-dioxaborolane 在 四(三苯基膦)钯 、 sodium carbonate 作用下， 以 乙醇 、 水 、 甲苯 为溶剂， 反应 0.17h， 以79%的产率得到2-(2-(methylthiomethyl)phenyl)-5-nitropyridine
  参考文献：
  名称：

  Microwave-Mediated Suzuki–Miyaura Cross-Couplings of Thioether- and ortho-Substituted Methylphenylboronic Acid Esters

  摘要：

  Hiterto unsuccessful cross-couplings of ortho-substituted or thioether-substituted methylphenylboronates have now been achieved, under microwave conditions, enabling the synthesis of a library of novel biaryls. Tetrakis(triphenylphosphine) palladium and various bases, for example, sodium carbonate or cesium fluoride, were found to mediate the crucial C-C bond-forming cross-coupling reaction.

  DOI：

  10.1055/s-0032-1317205
• 作为产物：
  描述：

  苄硫醇 在 5-甲基-2-(噻吩-3-基)吡啶 、 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 、 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 23.78h， 生成 4,4,5,5-tetramethyl-2-(2-((methylthio)methyl)phenyl)-1,3,2-dioxaborolane
  参考文献：
  名称：

  用于定向 C(sp2)–H 和 C(sp3)–H 硼酸化不同类型底物的显着高效铱催化剂

  摘要：

  在这里，我们描述了一类新的 C-H 硼化催化剂的发现及其在芳族、杂芳族和脂肪族系统的区域选择性 C-H 硼化中的应用。新催化剂具有 Ir-C(噻吩基) 或 Ir-C(呋喃基) 阴离子配体，而不是标准 C-H 硼化条件中使用的二胺型中性螯合配体。据报道，这些新发现的催化剂的使用对不同种类的芳烃底物显示出优异的反应性和邻位选择性，并具有高分离产率。此外，该催化剂被证明对大量脂肪族底物的选择性 C(sp 3)–H 键硼化。杂环分子利用 C-H 键固有的高反应性选择性地硼化。已经使用相同的催化剂描述了许多后期 C-H 功能化。此外，我们表明其中一种催化剂甚至可以在露天用于 C(sp 2 )-H 和 C(sp 3 )-H 硼酸化，从而使该方法更加通用。初步的机理研究表明，活性催化中间体是 Ir(bis)boryl 络合物，连接的配体作为双齿配体。总的来说，这项研究强调了新型 C-H 硼酸化催化剂的发现，这些催化剂应该在

  DOI：

  10.1021/jacs.0c13415

文献信息

• COMT INHIBITORS
  申请人：Hoffmann-La Roche Inc.

  公开号：US20160002177A1

  公开（公告）日：2016-01-07

  The present invention relates to compounds of formula wherein the substituents are described in claim 1 and to the pharmaceutically acceptable salts thereof. These compounds inhibit the enzyme catechol-O-methyltransferase (COMT). The compounds may be used for the treatment of Parkinson's disease, depression, cognitive impairment and motor symptoms, resistant depression, cognitive impairment, mood and negative symptoms of schizophrenia.

  本发明涉及式中所述的化合物，其中取代基在权利要求书1中描述，并且其药学上可接受的盐。这些化合物抑制酶儿茶酚-O-甲基转移酶（COMT）。这些化合物可用于治疗帕金森病、抑郁症、认知障碍和运动症状、难治性抑郁症、认知障碍、情绪和精神分裂症的负面症状。
• Synthesis of ortho-modified mercapto- and piperazino-methyl-phenylboronic acid derivatives
  作者：John Spencer、Andrew P. Burd、Christopher A. Goodwin、Sandrine A.M. Mérette、Michael F. Scully、Trushar Adatia、John J. Deadman

  DOI：10.1016/s0040-4020(01)01028-6

  日期：2002.2

  The synthesis of 2-mercapto- and 2-piperazino- (methyl-phenyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolanes 4 and 5, respectively, is described and their inhibitory activity against serine proteases including thrombin was measured. Some of these compounds were studied in both the solid state and in solution, displaying no S-B coordination and only weak N-B coordination. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Microwave-Mediated Synthesis of an Arylboronate Library
  作者：John Spencer、Christine B. Baltus、Hiren Patel、Neil J. Press、Samantha K. Callear、Louise Male、Simon J. Coles

  DOI：10.1021/co100011g

  日期：2011.1.10

  A series of arylboronates has been synthesized from the reaction of 2-(2-, (3-, or (4-(bromomethyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 11-3) respectively with a range of N-, S-, and O-nucleophiles, using microwave-mediated chemistry. For the synthesis of N- and S-substituted boronates, a supported base, PS-NMM, was employed, and many reactions were complete within 15 min. With O-nucleophiles, a mixture of tetrabutylammonium bromide, potassium carbonate, and sodium hydroxide was employed. The resulting aminomethyl, mercaptomethyl, or alkoxy-/phenoxymethyl-arylboronates were subjected to microwave-mediated Suzuki Miyaura coupling reactions to afford a range of biaryls in moderate to good yields. The X-ray structures of five boronates were determined.
• Sulfur-Directed Ligand-Free C–H Borylation by Iridium Catalysis
  作者：Li Liu、Guanghui Wang、Jiao Jiao、Pengfei Li

  DOI：10.1021/acs.orglett.7b03008

  日期：2017.11.17

  An iridium-catalyzed ortho C-H borylation reaction directed by;cyclic dithioacetal moiety is disclosed. A series of borylation products were obtained in moderate to good yields under mild conditions in exclusive mono- and ortho-regioselectivity. Thus, the 1,3-dithiane or 1,3-dithiolane group serves as a remarkable effective directing group for C-H borylation without any ligand assistance. The further transformations of the borylation products are also carried out to change boryl group to other functional groups.
• Iridium-Catalyzed <i>ortho</i>-C–H Borylation of Thioanisole Derivatives Using Bipyridine-Type Ligand
  作者：Jialin Zeng、Morio Naito、Takeru Torigoe、Masahiro Yamanaka、Yoichiro Kuninobu

  DOI：10.1021/acs.orglett.0c00946

  日期：2020.5.1

  A simple iridium catalytic system was developed that allows for a variety of 2-borylthioanisoles to be easily synthesized via ortho-selective C-H borylation of thioanisole derivatives. Once introduced, boryl and methylthio groups were converted by palladium-catalyzed transformations. Density functional theory calculations revealed that weak interactions, such as hydrogen bonding between the C-H bond of the SCH3 group and the oxygen atom of the boryl ligand, control the ortho-selectivity.