碘甲基硼酸频哪醇酯 | 70557-99-2

• 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: 碘甲基硼酸频哪醇酯
• 中文别名: 2-碘甲基-4,4,5,5-四甲基-1,3,2-二氧硼戊环
• 英文名称: 2-(iodomethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: iodomethylboronic acid pinacol ester；iodomethylboronyl pinacolate；pinacol (iodomethyl)boronate；iodo methyl pinacol boronate；2-(iodomethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolan
• CAS: 70557-99-2
• 化学式: C₇H₁₄BIO₂
• 分子量: 267.902
• InChiKey: UBNNPAYFVZFWPE-UHFFFAOYSA-N

物化性质

• 沸点：
  64-65 °C(Press: 0.2 Torr)
• 密度：
  1.47±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.05
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 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
• 包装等级：
  III
• 危险类别：
  8
• 危险性防范说明：
  P280,P305+P351+P338,P310
• 危险品运输编号：
  1760
• 危险性描述：
  H302,H314
• 储存条件：
  2-8°C

SDS

Material Safety Data Sheet

---

Section 1. Identification of the substance
Product Name: Iodomethylboronic acid, pinacol ester
Synonyms: 2-(Iodomethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

---

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

---

Section 3. Composition/information on ingredients.
Ingredient name: Iodomethylboronic acid, pinacol ester
CAS number: 70557-99-2

---

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.

---

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.

---

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.

---

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:

---

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.

---

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: C7H14BIO2
Molecular weight: 267.9

---

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

---

Section 11. Toxicological information
No data.

---

Section 12. Ecological information
No data.

---

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.

---

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

---

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.

---

SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  碘甲基硼酸频哪醇酯 在 正丁基锂 作用下， 以 乙腈 为溶剂， 反应 17.33h， 生成 2,2'-(2-methyl-2-(naphthalen-2-yl)pentane-1,5-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)
  参考文献：
  名称：

  通过硼酸酯诱导的连续1,2迁移连续合成1,3-双-（硼基）烷烃。

  摘要：

  介绍了一种制备1,3-双（硼基）烷烃的通用有效方法。结果表明，易于生成的乙烯基硼酸酯络合物与市售的ICH 2 Bpin反应生成有价值的1,3-双-（硼基）烷烃。引入的转化在实验上易于进行，显示出广泛的底物范围和较高的官能团耐受性。机理研究表明，该反应不是通过自由基中间体进行的。取而代之的是，提出了前所未有的硼酸酯诱导的连续bis-1,2-迁移级联反应。

  DOI：

  10.1002/anie.202007541
• 作为产物：
  描述：

  溴甲基苯甲酸频那酯 在 sodium iodide 作用下， 以 丙酮 为溶剂， 以97%的产率得到碘甲基硼酸频哪醇酯
  参考文献：
  名称：

  直接光获取 α-硼基自由基：在烯丙基硼酯立体发散合成中的应用**

  摘要：

  α-硼基自由基作为多功能中间体重新出现，通过相邻的 C−C 键形成来获取有机硼。我们公开了使用光和路易斯碱轻松活化α-卤代硼酸酯以允许均裂。添加到苯乙烯中可以构建E-烯丙基硼酸酯。活化的简单性允许与能量转移催化的战略合并，从而实现Z异构体的立体发散合成。

  DOI：

  10.1002/anie.202307540

文献信息

• Diboration of 3-substituted propargylic alcohols using a bimetallic catalyst system: access to (<i>Z</i>)-allyl, vinyldiboronates
  作者：Cheryl L. Peck、Jan Nekvinda、Webster L. Santos

  DOI：10.1039/d0cc03563g

  日期：——

  A Pd/Cu catalyst system facilitates the diboration of unactivated propargylic alcohols with pentafluoroboronic acid and diboron to generate (Z)-allyl, vinyldiboronates.

  一种Pd/Cu催化剂体系促进了未活化的丙炔醇与五氟硼酸和二硼烷的二硼化反应，生成(Z)-烯丙基、烯基二硼酸酯。
• Stereoselective Access to Alkylidenecyclobutanes through γ-Selective Cross-Coupling Strategies
  作者：Michael Eisold、Dorian Didier

  DOI：10.1021/acs.orglett.7b01803

  日期：2017.8.4

  Alkylidenecyclobutanes (ACBs) containing all-carbon quaternary stereocenters were simply and efficiently synthesized by combining boron-homologation and γ-selective cross-coupling strategies. This unique sequence led to excellent regio- and diastereoselectivities in the generation of targeted four-membered rings with up to 99% enantiomeric excess using chiral substrates. In addition to the original

  通过结合硼-同系物和γ-选择性交叉偶联策略，可以简单有效地合成含有全碳四元立体中心的亚烷基亚环丁烷（ACB）。这种独特的序列在使用手性底物产生具有高达99％对映体过量的靶向四元环时，产生了极好的区域选择性和非对映选择性。除了ACB的原始合成以外，最后还显示了基于γ-选择性交叉偶联反应的四元立体中心的第一个不对称催化形成。
• Site-Selective C–H alkylation of Complex Arenes by a Two-Step Aryl Thianthrenation-Reductive Alkylation Sequence
  作者：Beatrice Lansbergen、Paola Granatino、Tobias Ritter

  DOI：10.1021/jacs.1c03459

  日期：2021.6.2

  undirected para-selective two-step C–H alkylation of complex arenes useful for late-stage functionalization. The combination of a site-selective C–H thianthrenation with palladium-catalyzed reductive electrophile cross-coupling grants access to a diverse range of synthetically useful alkylated arenes which cannot be accessed otherwise with comparable selectivity, diversity, and practicality. The robustness

  在此，我们提出了复杂芳烃的非定向对位选择性两步C-H烷基化，可用于后期功能化。位点选择性 C-H 噻蒽醌化与钯催化的还原亲电试剂交叉偶联相结合，可以得到多种合成上有用的烷基化芳烃，而这些烷基化芳烃是无法以其他方式获得的，具有相当的选择性、多样性和实用性。两个复杂片段的基于铊的还原偶联进一步证明了这种转化的稳健性。
• Novel Isomerically Pure Tetrasubstituted Allylboronates:  Stereocontrolled Synthesis of α-Exomethylene γ-Lactones as Aldol-Like Adducts with a Stereogenic Quaternary Carbon Center
  作者：Jason W. J. Kennedy、Dennis G. Hall

  DOI：10.1021/ja016391e

  日期：2002.2.1

  1-alkoxycarbonyl vinylcopper(I) intermediates from the conjugate addition of organocuprates onto acetylenic esters were trapped with very high cis-addition selectivity with iodomethylboronic esters in the presence of HMPA. The resulting isomerically pure 3,3-disubstituted allylboronates react with aldehydes in a highly diastereo- and enantioselective manner, providing α-exomethylene γ-lactones with a stereogenic

  尽管它们固有的异构化倾向和低反应性，1-烷氧基羰基乙烯基铜 (I) 中间体在 HMPA 存在下与碘甲基硼酸酯以非常高的顺式加成选择性捕获了有机铜酸盐与炔酸酯的共轭加成。所得的异构纯 3,3-二取代烯丙基硼酸酯以高度非对映选择性和对映选择性方式与醛反应，提供具有立体异构四元 β-碳中心的 α-外亚甲基 γ-内酯。
• Lewis Acid Catalyzed Allylboration:  Discovery, Optimization, and Application to the Formation of Stereogenic Quaternary Carbon Centers
  作者：Jason W. J. Kennedy、Dennis G. Hall

  DOI：10.1021/jo049773m

  日期：2004.6.1

  A full account of the development of the first catalytic manifold for the additions of allylboronates to aldehydes is described. The thermal additions (both diastereospecific and enantioselective) of 2-carboxyester 3,3-disubstituted allylboronates 1 to both aromatic and aliphatic aldehydes give biologically and synthetically important exo-methylene butyrolactones 2 containing a β-quaternary carbon

  描述了将烯丙基硼酸酯加成到醛中的第一催化歧管的发展的完整说明。将2-羧酸酯3,3-二取代的烯丙基硼酸酯1热加成（非对映体特异性和对映体选择性）对芳香族和脂肪族醛均具有生物学和合成意义的外亚甲基丁内酯2包含一个β-季碳中心。尽管热反应在室温下需要14 d才能完成，但是某些金属盐的存在可以使反应12-16 h，同时保留未催化过程中观察到的非对映特异性。描述了对催化作用起源的初步机理研究，以及内酯2立体选择性转化为环状和非环状的立体三单元体，具有潜在的合成中间体用途。