1-环庚烯-1-硼酸频哪醇酯 | 287944-13-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 中文名称: 1-环庚烯-1-硼酸频哪醇酯
• 英文名称: 2-(cyclohept-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: 2-(cyclohepten-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 287944-13-2
• 化学式: C₁₃H₂₃BO₂
• 分子量: 222.135
• InChiKey: XCKJXFSLFZYWSB-UHFFFAOYSA-N

物化性质

• 沸点：
  253.0±33.0 °C(Predicted)
• 密度：
  0.94±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.51
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2934999090

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: 1-Cycloheptenylboronic acid pinacol ester
Synonyms:

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Section 2. Hazards identification
Harmful by inhalation, in contact with skin, and if swallowed.

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Section 3. Composition/information on ingredients.
Ingredient name: 1-Cycloheptenylboronic acid pinacol ester
CAS number: 287944-13-2

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Section 4. First aid measures
Skin contact: Immediately wash skin with copious amounts of water for at least 15 minutes while removing
contaminated clothing and shoes. If irritation persists, seek medical attention.
Eye contact: Immediately wash skin with copious amounts of water for at least 15 minutes. Assure adequate
flushing of the eyes by separating the eyelids with fingers. If irritation persists, seek medical
attention.
Inhalation: Remove to fresh air. In severe cases or if symptoms persist, seek medical attention.
Ingestion: Wash out mouth with copious amounts of water for at least 15 minutes. Seek medical attention.

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Section 5. Fire fighting measures
In the event of a fire involving this material, alone or in combination with other materials, use dry
powder or carbon dioxide extinguishers. Protective clothing and self-contained breathing apparatus
should be worn.

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Section 6. Accidental release measures
Personal precautions: Wear suitable personal protective equipment which performs satisfactorily and meets local/state/national
standards.
Respiratory precaution: Wear approved mask/respirator
Hand precaution: Wear suitable gloves/gauntlets
Skin protection: Wear suitable protective clothing
Eye protection: Wear suitable eye protection
Methods for cleaning up: Mix with sand or similar inert absorbent material, sweep up and keep in a tightly closed container
for disposal. See section 12.
Environmental precautions: Do not allow material to enter drains or water courses.

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Section 7. Handling and storage
Handling: This product should be handled only by, or under the close supervision of, those properly qualified
in the handling and use of potentially hazardous chemicals, who should take into account the fire,
health and chemical hazard data given on this sheet.
Store in closed vessels, under −20◦C.
Storage:

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Section 8. Exposure Controls / Personal protection
Engineering Controls: Use only in a chemical fume hood.
Personal protective equipment: Wear laboratory clothing, chemical-resistant gloves and safety goggles.
General hydiene measures: Wash thoroughly after handling. Wash contaminated clothing before reuse.

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Section 9. Physical and chemical properties
Appearance: Not specified
Boiling point: No data
No data
Melting point:
Flash point: No data
Density: No data
Molecular formula: C13H23BO2
Molecular weight: 222.1

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Section 10. Stability and reactivity
Conditions to avoid: Heat, flames and sparks.
Materials to avoid: Oxidizing agents.
Possible hazardous combustion products: Carbon monoxide.

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Section 11. Toxicological information
No data.

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Section 12. Ecological information
No data.

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Section 13. Disposal consideration
Arrange disposal as special waste, by licensed disposal company, in consultation with local waste
disposal authority, in accordance with national and regional regulations.

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Section 14. Transportation information
Non-harzardous for air and ground transportation.

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Section 15. Regulatory information
No chemicals in this material are subject to the reporting requirements of SARA Title III, Section
302, or have known CAS numbers that exceed the threshold reporting levels established by SARA
Title III, Section 313.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  1-环庚烯-1-硼酸频哪醇酯 在 sodium periodate 、 ammonium acetate 作用下， 以 水 、 丙酮 为溶剂， 生成 环庚烯-1-基硼酸
  参考文献：
  名称：

  通过烯基硼酸的羰基化作用中断的菲舍尔-吲哚中间体

  摘要：

  在铜介导的和铜催化的条件下，已经实现了烯基硼酸与N-芳基苯并异羟肟酸的氧化芳基化，以提供接近的费歇尔-吲哚中间体的途径。据认为，这种转变是通过铜促进的C–O键形成事件继之以[3,3]重排而进行的。描述了该方法的范围并讨论了机械实验。

  DOI：

  10.1021/ol401416r
• 作为产物：
  描述：

  环庚酮 在 2-氯吡啶 、 chromium chloride 、 magnesium 、 4,4'-二叔丁基-2,2'-二吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 18.17h， 生成 1-环庚烯-1-硼酸频哪醇酯
  参考文献：
  名称：

  三氟甲磺酸乙烯酯和未活化芳基羧酸酯与频哪醇硼烷的铬催化选择性硼化

  摘要：

  使用频哪醇硼烷对丰富的乙烯基三氟甲磺酸酯和未活化的芳基羧酸酯进行硼酸化是通过铬催化选择性形成乙烯基和芳基硼酸酯实现的。竞争性氢化还原或烯丙基硼化反应缓慢或不发生，因此为将硼酸盐结合到烯烃和芳烃中提供了一种选择性策略。机理研究表明，σ键复分解或氧化加成机制可能被认为是酯支架断裂的原因。

  DOI：

  10.1021/acs.orglett.2c01015

文献信息

• Palladium-Catalyzed Cross-Coupling Reaction of Bis(pinacolato)diboron with 1-Alkenyl Halides or Triflates:  Convenient Synthesis of Unsymmetrical 1,3-Dienes via the Borylation-Coupling Sequence
  作者：Jun Takagi、Kou Takahashi、Tatsuo Ishiyama、Norio Miyaura

  DOI：10.1021/ja0202255

  日期：2002.7.1

  1-alkenylboronic acid pinacol esters via a palladium-catalyzed cross-coupling reaction of bis(pinacolato)diboron (pin(2)B(2), pin = Me(4)C(2)O(2)) with 1-alkenyl halides or triflates was carried out in toluene at 50 degrees C in the presence of KOPh (1.5 equiv) and PdCl(2)(PPh(3))(2)-2Ph(3)P (3 mol %). The borylation of acyclic and cyclic 1-alkenyl bromides and triflates was achieved in high yields with complete

  通过钯催化的双（频哪醇）二硼（pin（2）B（2），pin = Me（4）C（2）O（2））的交叉偶联反应合成1-烯基硼酸频哪醇酯在 KOPh（1.5 当量）和 PdCl(2)(PPh(3))(2)-2Ph(3)P (3 mol%) 的存在下，1-烯基卤化物或三氟甲磺酸酯在 50 摄氏度的甲苯中进行。无环和环状 1-烯基溴化物和三氟甲磺酸酯的硼化反应以高产率实现，并完全保留了双键的构型。该方法通过硼酸化偶联序列应用于不对称1,3-二烯的一锅法合成。
• [EN] MTH1 INHIBITORS FOR TREATMENT OF CANCER<br/>[FR] INHIBITEURS MTH1 POUR LE TRAITEMENT DU CANCER
  申请人：THOMAS HELLEDAYS STIFTELSE FÖR MEDICINSK FORSKNING

  公开号：WO2015187088A1

  公开（公告）日：2015-12-10

  A compound of formula I, (I) or a pharmaceutically-acceptable salt thereof. The compound is useful in the treatment of cancer.

  公式I的化合物(I)或其药用可接受的盐。该化合物在治疗癌症中很有用。
• Development and Mechanistic Studies of Iron-Catalyzed Construction of Csp²–B Bonds via C–O Bond Activation
  作者：Shasha Geng、Juan Zhang、Shuo Chen、Zhengli Liu、Xiaoqin Zeng、Yun He、Zhang Feng

  DOI：10.1021/acs.orglett.0c01937

  日期：2020.7.17

  Herein we describe an iron-catalyzed borylation of alkenyl and aryl carbamates through the activation of a C–O bond. This protocol exhibits high efficiency, a broad substrate scope, and the late-stage borylation of biorelevant compounds, thus providing potential applications in medicinal chemistry. Moreover, this method enables orthogonal transformations of phenol derivatives and also offers good opportunities

  在本文中，我们描述了通过C-O键的活化，铁催化的烯基和芳基氨基甲酸酯的硼酸酯化反应。该方案显示出高效率，广泛的底物范围以及生物相关化合物的后期硼化，因此在药物化学中提供了潜在的应用。而且，该方法能够使酚衍生物进行正交转化，并且还为合成多取代的芳烃提供了良好的机会。初步的机理研究表明，通过自由基途径的Fe II / Fe III催化循环可能与反应有关。
• [EN] MTH1 INHIBITORS FOR TREATMENT OF INFLAMMATORY AND AUTOIMMUNE CONDITIONS<br/>[FR] INHIBITEURS DE MTH1 DESTINÉS AU TRAITEMENT DES ÉTATS INFLAMMATOIRES ET AUTO-IMMUNS
  申请人：THOMAS HELLEDAYS STIFTELSE FÖR MEDICINSK FORSKNING

  公开号：WO2015187089A1

  公开（公告）日：2015-12-10

  A compound of formula (I), or a pharmaceutically acceptable salt thereof, for use in the treatment of autoimmune diseases and inflammatory conditions.

  化合物的化学式（I），或其药学上可接受的盐，用于治疗自身免疫性疾病和炎症性疾病。
• PSiP-Pincer Type Palladium-Catalyzed Dehydrogenative Borylation of Alkenes and 1,3-Dienes
  作者：Naohiro Kirai、Shoichiro Iguchi、Tatsuyoshi Ito、Jun Takaya、Nobuharu Iwasawa

  DOI：10.1246/bcsj.20130004

  日期：2013.7.15

  Dehydrogenative borylation of alkenes and 1,3-dienes was realized by carrying out the reaction in the presence of bis(pinacolato)diboron (B2pin2) and a catalytic amount of PSiP-pincer palladium complex. This protocol has the following notable features. 1) Monoanionic nature of the PSiP-pincer ligand prevents the formation of boryl(hydrido)- or dihydridopalladium species, enabling synthesis of various vinyl- or dienylboronic esters in good yield from a 1:1 mixture of B2pin2 and alkenes or 1,3-dienes without forming hydroboration or hydrogenation products. 2) Due to the strong trans influence of the silicon atom, PSiP-pincer palladium complex showed high activity toward migratory insertion. 3) Suppression of these side-reactions and the high reactivity of the PSiP-pincer palladium complex enabled an efficient, successive dehydrogenative borylation to give 1,1- or 1,2-diborylated products depending on the kind of substituent on alkenes by using more than 2 equivalents of B2pin2. Mechanistic study revealed that PSiP-pincer borylpalladium complex was generated from hydridopalladium complex and B2pin2, and this complex underwent alkene insertion followed by β-hydride elimination to give alkenylboronic ester with regeneration of the hydridopalladium complex.

  通过在双(频哪醇)二硼(B2pin2)和催化量的PSiP-螯合钯配合物存在下进行反应，实现了烯烃和1,3-二烯的脱氢硼化反应。该方案具有以下显著特点：1) PSiP-螯合配体的单阴离子性质阻止了硼(氢)化物或二氢化钯物种的形成，从而能够从B2pin2和烯烃或1,3-二烯的1:1混合物中以良好的产率合成各种乙烯基或二烯基硼酸酯，而不形成氢硼化或氢化产物。2) 由于硅原子的强横向影响，PSiP-螯合钯配合物显示出高的迁移插入活性。3) 抑制这些副反应和PSiP-螯合钯配合物的高反应性使得高效连续脱氢硼化反应成为可能，从而根据烯烃上取代基的种类，使用超过2当量的B2pin2，生成1,1-或1,2-二硼化产物。机理研究表明，PSiP-螯合硼化钯配合物由氢化钯配合物和B2pin2生成，该配合物经过烯烃插入和β-氢消除，生成烯基硼酸酯，并再生氢化钯配合物。