-(3,3-dimethyl-1-buten-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 154820-99-2

• 物质功能分类: 医药中间体 - 原料药中间体
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: -(3,3-dimethyl-1-buten-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: (E)-2-(3,3-dimethylbut-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane；2-(3,3-dimethylbut-1-enyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 154820-99-2
• 化学式: C₁₂H₂₃BO₂
• 分子量: 210.124
• InChiKey: VTGDQOPDGQPGRO-UHFFFAOYSA-N

物化性质

• 熔点：
  38-43 °C
• 沸点：
  212.8±23.0 °C(Predicted)
• 密度：
  0.88±0.1 g/cm3(Predicted)
• 闪点：
  83 °C

计算性质

• 辛醇/水分配系数(LogP)：
  3.22
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2931900090
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  -20°C，保存于惰性气体中

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: 2-t-Butyl-E-vinylboronic 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: 2-t-Butyl-E-vinylboronic acid, pinacol ester
CAS number: 154820-99-2

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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, refrigerated.
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: C12H23BO2
Molecular weight: 210.1

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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：

  -(3,3-dimethyl-1-buten-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 potassium fluoride 、 6,6'-二甲基-2,2'-联吡啶 、 sodium perborate tetrahydrate 、 三乙氧基硅烷 、 nickel(II) bromide 2-methoxyethyl ether complex 作用下， 以 四氢呋喃 、 N,N-二甲基乙酰胺 、 水 、 乙腈 为溶剂， 反应 27.0h， 生成 C₁₂H₂₂O
  参考文献：
  名称：

  镍催化烯基硼酸酯的高选择性加氢烯基化反应，以得到烯丙基硼

  摘要：

  烯丙基硼衍生物是天然产物和生物活性分子合成中的重要组成部分。本文中，开发了镍催化的烯基硼酸酯的高选择性加氢烯基化的实用策略。在温和的反应条件下，可以得到具有优异的化学和区域选择性的各种烯丙基硼酸酯。通过控制实验和动力学研究说明了这种转化的机理。

  DOI：

  10.1021/acs.orglett.0c02923
• 作为产物：
  描述：

  3,3-二甲基-1-丁炔 、 频那醇硼烷 在 [RuHCl(CO)(PPh₃)₃] 作用下， 以 四氢呋喃 为溶剂， 生成 -(3,3-dimethyl-1-buten-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  铜介导的环状硫醚与硼化合物的解构环裂解

  摘要：

  环状硫醚的解构环裂解是通过硼化合物的 Chan-Lam 型过程实现的。炔烃的连续硼氢化/开环过程为基于开发条件的乙烯基硫化物的制备提供了一条新途径。进一步的探索证明了亲核试剂的多功能性，提供各种具有线性框架的功能化硫化物。

  DOI：

  10.1021/acs.orglett.3c01100

文献信息

• The Twisted Side Chain of Antillatoxin is Important for Potent Toxicity: Total Synthesis and Biological Evaluation of Antillatoxin and Analogues
  作者：Ken Okura、Shigeru Matsuoka、Ryosuke Goto、Masayuki Inoue

  DOI：10.1002/anie.200905892

  日期：2010.1.8

  Side‐chain plays lead role: Antillatoxin is a cyclic peptide and potent neurotoxin, and the total syntheses and biological evaluations of antillatoxin and its side‐chain analogues are reported. A subtle side‐chain modification led to dramatic changes in the cytotoxicity; detailed conformational analyses revealed that the shape of the twisted side chain is critical for the biological activity of antillatoxin

  侧链起着主导作用：抗毒素是一种环状肽和强效神经毒素，据报道，抗llato毒素及其侧链类似物的总合成和生物学评价。细微的侧链修饰导致细胞毒性发生巨大变化。详细的构象分析表明，扭曲的侧链的形状对于抗llatoxin的生物活性至关重要。
• Chemoselective Cross-Coupling of <i>gem</i>-Borazirconocene Alkanes with Aryl Halides
  作者：Chao Yang、Yadong Gao、Songlin Bai、Chao Jiang、Xiangbing Qi

  DOI：10.1021/jacs.0c03821

  日期：2020.7.1

  chemoselective conversion of the carbon-metal bond of gem-dimetallic reagents enables rapid and sequential formation of multiple carbon-carbon and carbon-heteroatom bonds, thus representing a powerful method for efficiently increasing structural complexity. Herein, we report a visible-light-induced, single nickel-catalyzed, chemoselective cross-coupling reaction between gem-borazirconocene alkanes and diverse

  宝石-双金属试剂的碳-金属键的直接和化学选择性转化能够快速、连续地形成多个碳-碳和碳-杂原子键，从而代表了一种有效增加结构复杂性的有效方法。在此，我们报告了一种可见光诱导的、单镍催化的、化学选择性交叉偶联的宝石-硼锆茂烷烃和多种芳基卤化物，以高产率提供了范围广泛的烷基 Bpin 衍生物，并具有出色的区域选择性。这种实用的方法具有非常简单的反应条件和广泛的底物范围。此外，我们系统地研究了 Bpin 导向的链行走过程，该过程是烷基二茂锆区域选择性的基础，从而揭示了用我们的方法实现的内烯烃远程官能化的机制。最后，DFT 计算表明该反应的高区域选择性源于 Bpin 基团的导向作用。
• Copper-catalyzed regioselective hydroboration of terminal alkynes in aqueous medium
  作者：Zi-Jian Yao、Shibin Hong、Wei Zhang、Mengyan Liu、Wei Deng

  DOI：10.1016/j.tetlet.2016.01.049

  日期：2016.2

  A mild and environment-friendly copper-catalyzed hydroboration of terminal alkynes in aqueous medium was reported. Regioselectivity control was achieved in the presence of cyclodextrin–bispyridine ligand (CD-1). This protocol was successfully applied to inactivated terminal alkynes. Moreover, the ligand was recovered and reused without any loss of activity over five cycles.

  据报道，在水性介质中温和且环保的末端炔烃铜催化的硼氢化反应。在存在环糊精-双吡啶配体（CD - 1）的情况下实现了区域选择性控制。该协议已成功应用于灭活的末端炔烃。此外，在五个循环中，该配体被回收并重新使用而没有任何活性损失。
• Catalysis-Based and Protecting-Group-Free Total Syntheses of the Marine Oxylipins Hybridalactone and the Ecklonialactones A, B, and C
  作者：Volker Hickmann、Azusa Kondoh、Barbara Gabor、Manuel Alcarazo、Alois Fürstner

  DOI：10.1021/ja204027a

  日期：2011.8.31

  for ring opening, this transformation had to be performed with complexes of the type [(Ar(3)SiO)(4)Mo≡CPh][K·OEt(2)] (43), which represent a new generation of exceedingly tolerant yet remarkably efficient catalysts. Their ancillary triarylsilanolate ligands temper the Lewis acidity of the molybdenum center but are not sufficiently nucleophilic to engage in the opening of the fragile epoxide ring. A

  开发了海洋 oxylipins 杂化内酯 (1) 和 ecklonialactone 家族的三个成员 (2-4) 的简洁且无保护基团的全合成。它们以最长的线性序列分别以 14 或 13 个步骤以光学纯形式传递这些目标；其中五个步骤是金属催化的，另外四个步骤是金属介导的。通往 1 或 2-4 的路线与常见的结构单元 22 不同，后者可通过 7 个步骤从 2[5H] 呋喃酮通过由香芹酮衍生的二烯控制的铑催化的不对称 1,4-加成反应获得配体35和由钌茚叉配合物17催化的闭环烯烃复分解（RCM）作为关键操作。或者，可以通过非对映选择性三组分偶联过程从糠醛中分 10 个步骤制备 22。将 22 进一步细化为具有七个连续手性中心的结构最复杂的目标杂化内酯是基于一系列环丙烷化，然后是钒催化的环氧化，两者都由 C15 上的相同游离羟基引导。大环支架通过闭环炔烃复分解反应（RCAM）与头基成环。为了响应目标
• Aliphatic α-Boryl-α-bromoketones: Synthesis and Reactivity
  作者：Yevhen M. Ivon、Yuliya O. Kuchkovska、Zoya V. Voitenko、Oleksandr O. Grygorenko

  DOI：10.1002/ejoc.202000078

  日期：2020.6.23

  Preparation of α‐boryl‐α‐bromoketones from alkenyl MIDA boronates bearing functionalized aliphatic derivatives is described. Ten examples of the target trifunctional boronate‐containing derivatives were obtained in up to 94 % yield over two steps.

  描述了从带有官能化脂肪族衍生物的链烯基MIDA硼酸盐制备α-硼基-α-溴代酮。在两个步骤中，以高达94％的产率获得了目标三官能含硼酸酯衍生物的十个实例。