5-甲氧基噻吩-2-硼酸频哪醇酯 | 596819-12-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 5-甲氧基噻吩-2-硼酸频哪醇酯
• 英文名称: 2-(5-methoxythiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: (5-methoxythiophen-2-yl)boronic acid pinacol ester；2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-methoxythiophene
• CAS: 596819-12-4
• 化学式: C₁₁H₁₇BO₃S
• 分子量: 240.131
• InChiKey: WAUOLRNNTGNWJP-UHFFFAOYSA-N

物化性质

• 沸点：
  332.7±27.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)
• 溶解度：
  氯仿（微溶）、乙酸乙酯（微溶）

计算性质

• 辛醇/水分配系数(LogP)：
  2.06
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  55.9
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 海关编码：
  2934999090
• 危险性防范说明：
  P261,P264,P270,P271,P280,P301+P312,P302+P352,P304+P340,P330,P363,P501
• 危险性描述：
  H302,H312,H332

反应信息

• 作为反应物：
  描述：

  5-甲氧基噻吩-2-硼酸频哪醇酯 在 bis-triphenylphosphine-palladium(II) chloride 、 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 potassium acetate 、 sodium carbonate 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 水 、 二甲基亚砜 为溶剂， 反应 14.5h， 生成 [4-(5-methoxythiophen-2-yl)phenyl]boronic acid pinacol ester
  参考文献：
  名称：

  3,4-Dinitrothiophene as a central unit of quadrupolar push-pull-push systems

  摘要：

  3,4-Dinitrothiophene has been utilized as a central acceptor unit in quadrupolar D-pi-A-pi-D push-pull-push chromophores. Employing cross-coupling and Knoevenagel reactions, nine novel chromophores bearing terminal methoxythiophene donor and systematically extended/varied pi-linker were synthesized. Optical properties were studied by electronic absorption spectra. Fundamental optoelectronic properties were investigated by semiempirical PM7 calculations. It was shown that by varying the pi-conjugated system the longestwavelength absorption maxima can be shifted from 341 to 489 nm. The calculated HOMO-LUMO gaps were found within the range of 6.69-7.29 eV, while the second-order molecular polarizabilities can be tuned from 0.038 to 1.578 x 10(-27) esu.

  DOI：

  10.1007/s10593-017-2020-1
• 作为产物：
  描述：

  2-甲氧基噻吩 在 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 、 1,3-二环己基氯化咪唑 、 sodium t-butanolate 作用下， 以 四氢呋喃 、 甲基环己烷 为溶剂， 反应 5.5h， 生成 5-甲氧基噻吩-2-硼酸频哪醇酯
  参考文献：
  名称：

  Iridium/N-heterocyclic carbene-catalyzed C–H borylation of arenes by diisopropylaminoborane

  摘要：

  芳烃的催化C-H硼化反应在有机合成中被广泛应用，因为它可以直接将多功能硼基引入简单的未官能化芳烃中。本文报道了在芳烃的C-H硼化反应中使用二异丙胺硼烷作为硼源。发现一种含有1,3-二环己基咪唑-2-基亚胺的铱(I)配合物能有效催化芳烃和杂环芳烃的硼化反应。所得的氨基硼化产物可以通过与适当的二醇或二胺处理简单地转化为相应的硼酸衍生物。

  DOI：

  10.3762/bjoc.12.65

文献信息

• Practical and Scalable Synthesis of Borylated Heterocycles Using Bench-Stable Precursors of Metal-Free Lewis Pair Catalysts
  作者：Arumugam Jayaraman、Luis C. Misal Castro、Frédéric-Georges Fontaine

  DOI：10.1021/acs.oprd.8b00248

  日期：2018.11.16

  A practical and scalable metal-free catalytic method for the borylation and borylative dearomatization of heteroarenes has been developed. This synthetic method uses inexpensive and conveniently synthesizable bench-stable precatalysts of the form 1-NHR2-2-BF3-C6H4, commercially and synthetically accessible heteroarenes as substrates, and pinacolborane as the borylation reagent. The preparation of several

  已开发出一种实用且可扩展的无杂芳烃的硼化和硼基脱芳香化的无金属催化方法。这种合成方法使用廉价且可方便合成的1-NHR 2 -2-BF 3 -C 6 H 4形式的台式稳定型预催化剂。，市售和合成途径可得到的杂芳烃作为底物，频哪醇硼烷作为硼化试剂。在无溶剂条件下，无需使用Schlenk技术或手套箱即可制备2和50 g规模的数个硼化杂环。使用这种经济高效的绿色方法还可以实现其中一种杂芳烃底物的公斤级硼化，这证明了我们的方法可以在精细化工行业中方便地实施的事实。
• Structural elaboration of dicyanopyrazine: towards push–pull molecules with tailored photoredox activity
  作者：Zuzana Hloušková、Milan Klikar、Oldřich Pytela、Numan Almonasy、Aleš Růžička、Veronika Jandová、Filip Bureš

  DOI：10.1039/c9ra04731j

  日期：——

  provided a series of catalysts based on a pyrazine heterocyclic scaffold with easy synthesis and further modification, diverse photoredox characteristics and wide application potential across modern photoredox transformations. The photoredox catalytic activities of the target catalysts were examined in a benchmark cross-dehydrogenative coupling and novel and challenging annulation reactions.

  作为成功的二氰基吡嗪光氧化还原催化剂的延伸，设计并轻松合成了一系列具有系统改变结构的X形推挽分子；它们的结构-性质关系通过以下方式详细阐明实验和理论计算。双氰基吡嗪被证明是一种强大的光氧化还原催化剂，具有推挽式排列，可以通过互换 D-π-A 系统的特定部分来轻松调整性能。改变氰基受体与甲氧基、甲硫基和噻吩基供体的相互位置以及修饰连接基可以广泛调整催化剂的基本性质。与目前可用的有机光氧化还原催化剂相反，我们提供了一系列基于吡嗪杂环支架的催化剂，具有易于合成和进一步改性、多种光氧化还原特性和在现代光氧化还原转化中的广泛应用潜力。
• [EN] PHENYL-SULFAMOYL.BENZOYC ACIDS AS ERAP1 MODULATORS<br/>[FR] ACIDES PHÉNYLSULFAMOYLBENZOÏQUES EN TANT QUE MODULATEURS D'ERAP1
  申请人：GREY WOLF THERAPEUTICS LTD

  公开号：WO2020225569A1

  公开（公告）日：2020-11-12

  The present invention relates to a compound of formula (I), or a pharmaceutically acceptable salt or hydrate thereof, wherein: the group X-Y is -NHSO2- or -SO2NH-; Z is a monocyclic aryl or heteroaryl group, each of which is optionally substituted by one ormore substituents selected from alkyl, cycloalkyl, halo, alkoxy, CN, haloalkyl and OH; R1 is H or alkyl; R2 is selected from COOH and a tetrazolyl group; R3 is selected from H, C land alkyl; R4 is selected from H and halo; R5 is selected from H, alkyl, haloalkyl, SO2-alkyl,Cl, alkoxy, OH, CN, hydroxyalkyl, alkylthio, heteroaryl, cycloalkyl, heterocycloalkyl andhaloalkoxy; R6 is H; R7 is selected from H, CN, haloalkyl, halo, SO2-alkyl,SO2NR12R13, heteroaryl, CONR10R11 and alkyl, wherein said heteroaryl group is optionallysubstituted by one or more substituents selected from alkyl, halo, alkoxy, CN, haloalkyl and OH; R8 is selected from H, alkyl, haloalkyl and halo; and R9 is H, alkyl or halo; R10 and R11 are each independently H or alkyl; and R12 and R13 are each independently H or alkyl. Further aspects of the invention relate to such compounds for use in the field of immuno- oncology and related applications. Another aspect of the invention relates to compounds of formulae (la) and (lb).

  本发明涉及一种具有式(I)的化合物，或其药学上可接受的盐或水合物，其中：基团X-Y为-NHSO2-或-SO2NH-；Z为单环芳基或杂环芳基，每个基团可选择地由一种或多种从烷基、环烷基、卤素、烷氧基、CN、卤代烷基和羟基中选择的取代基取代；R1为H或烷基；R2从COOH和四唑基团中选择；R3从H、C和烷基中选择；R4从H和卤素中选择；R5从H、烷基、卤代烷基、SO2-烷基、Cl、烷氧基、OH、CN、羟基烷基、烷基硫、杂环芳基、环烷基、杂环烷基和卤代烷氧基中选择；R6为H；R7从H、CN、卤代烷基、卤素、SO2-烷基、SO2NR12R13、杂环芳基、CONR10R11和烷基中选择，其中所述的杂环芳基可选择地由一种或多种从烷基、卤素、烷氧基、CN、卤代烷基和羟基中选择的取代基取代；R8从H、烷基、卤代烷基和卤素中选择；R9为H、烷基或卤素；R10和R11各自独立地为H或烷基；R12和R13各自独立地为H或烷基。本发明的进一步方面涉及这些化合物在免疫肿瘤学领域及相关应用中的用途。本发明的另一个方面涉及式(la)和(lb)的化合物。
• Iridium/N-heterocyclic carbene-catalyzed C–H borylation of arenes by diisopropylaminoborane
  作者：Mamoru Tobisu、Takuya Igarashi、Naoto Chatani

  DOI：10.3762/bjoc.12.65

  日期：——

  Catalytic C–H borylation of arenes has been widely used in organic synthesis because it allows the introduction of a versatile boron functionality directly onto simple, unfunctionalized arenes. We report herein the use of diisopropylaminoborane as a boron source in C–H borylation of arenes. An iridium(I) complex with 1,3-dicyclohexylimidazol-2-ylidene is found to efficiently catalyze the borylation of arenes and heteroarenes. The resulting aminoborylated products can be converted to the corresponding boronic acid derivatives simply by treatment with suitable diols or diamines.

  芳烃的催化C-H硼化反应在有机合成中被广泛应用，因为它可以直接将多功能硼基引入简单的未官能化芳烃中。本文报道了在芳烃的C-H硼化反应中使用二异丙胺硼烷作为硼源。发现一种含有1,3-二环己基咪唑-2-基亚胺的铱(I)配合物能有效催化芳烃和杂环芳烃的硼化反应。所得的氨基硼化产物可以通过与适当的二醇或二胺处理简单地转化为相应的硼酸衍生物。
• Organophosphorus-catalyzed relay oxidation of H-Bpin: electrophilic C–H borylation of heteroarenes
  作者：Jeffrey M. Lipshultz、Yue Fu、Peng Liu、Alexander T. Radosevich

  DOI：10.1039/d0sc05620k

  日期：——

  phosphorus triamide (1, PN[o-NMe-C6H4]2}) is shown to catalyze C–H borylation of electron-rich heteroarenes with pinacolborane (HBpin) in the presence of a mild chloroalkane reagent. C–H borylation proceeds for a range of electron-rich heterocycles including pyrroles, indoles, and thiophenes of varied substitution. Mechanistic studies implicate an initial P–N cooperative activation of HBpin by 1 to give

  在温和的氯代烷试剂存在下，非三角磷三酰胺 ( 1 , PN[ o -NMe-C 6 H 4 ] 2 }) 可催化富电子杂芳烃与频哪醇硼烷 (HBpin) 的 C-H 硼化反应。对于一系列富电子杂环，包括不同取代的吡咯、吲哚和噻吩，进行 C-H 硼化。机理研究表明HBpin的初始 P-N 协同活化由1产生P-氢化二氮杂膦2，其被 Atherton-Todd 氧化与氯代烷转移以产生P-氯二氮杂膦3. DFT 计算表明频哪醇硼烷随后被3氧化生成氯频哪醇硼烷 (ClBpin) 作为瞬态亲电硼化物质，与观察到的取代基效应和区域化学结果一致。这些结果说明了有机磷催化中已建立的反应途径的目标转移，以实现主基团催化的 C-H 硼化的新模式。