3-(4,4,5,5-四甲基-[1,3,2]二氧杂环戊硼烷-2-基)丙酸乙酯 | 302577-73-7

• 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
• 中文名称: 3-(4,4,5,5-四甲基-[1,3,2]二氧杂环戊硼烷-2-基)丙酸乙酯
• 中文别名: 乙基3-(4,4,5,5-四甲基-[1,3,2]二氧杂环戊硼烷-2-基)丙酸酯
• 英文名称: ethyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanoate
• 英文别名: ethyl 3-(4,4,5,5,-tetramethyl-[1,3,2]dioxaborolan-2-yl)-propionate
• CAS: 302577-73-7
• 化学式: C₁₁H₂₁BO₄
• 分子量: 228.096
• InChiKey: OSBBNOTZLRIDPR-UHFFFAOYSA-N

物化性质

• 沸点：
  261.7±23.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.03
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: 2-(Ethoxycarbonyl)ethylboronic acid, pinacol ester
Synonyms: Ethyl 3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)proprionate

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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-(Ethoxycarbonyl)ethylboronic acid, pinacol ester
CAS number: 302577-73-7

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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: C11H21BO4
Molecular weight: 228.1

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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-(4,4,5,5-四甲基-[1,3,2]二氧杂环戊硼烷-2-基)丙酸乙酯 在 二氟化氢钾 作用下， 以 水 、 乙腈 为溶剂， 反应 3.0h， 以136 mg的产率得到potassium 3-trifluoroboratopropionate ethyl ester
  参考文献：
  名称：

  Suzuki−Miyaura Cross-Coupling of Potassium Trifluoroboratohomoenolates

  摘要：

  Ketone-, ester-, and amide-containing potassium trifluoroboratohomoenolates were prepared in good to excellent yields from the corresponding unsaturated carbonyl compounds. They were shown to be effective coupling partners in the Suzuki-Miyaura reaction with a variety of electrophiles including electron-rich and electron-poor aryl bromides and -chlorides.

  DOI：

  10.1021/ol800357c
• 作为产物：
  描述：

  联硼酸频那醇酯 、 丙烯酸乙酯 在 双(2-二苯基磷苯基)醚 、 copper(l) chloride 甲醇 、 sodium t-butanolate 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以98%的产率得到3-(4,4,5,5-四甲基-[1,3,2]二氧杂环戊硼烷-2-基)丙酸乙酯
  参考文献：
  名称：

  铜催化的α-β-不饱和羰基化合物的β-硼酸化：通过醇类添加剂的速率加速。

  摘要：

  [反应：见正文]已经使用铜-二膦催化剂将双（频哪醇）二硼有效地添加到α，β-不饱和羰基化合物中。通过添加醇类添加剂，可以显着加快反应速度。使用该方法，使各种α，β-不饱和羰基化合物，包括在酸氧化水平上的共轭底物，如酯和腈，进行反应，以高收率得到相应的β-硼烷基羰基化合物。

  DOI：

  10.1021/ol061955a

文献信息

• A General Approach to Deboronative Radical Chain Reactions with Pinacol Alkylboronic Esters
  作者：Emy André‐Joyaux、Andrey Kuzovlev、Nicholas D. C. Tappin、Philippe Renaud

  DOI：10.1002/anie.202004012

  日期：2020.8.10

  suitable substrates. We report their in situ conversion into alkylboronic catechol esters by boron‐transesterification with a substoichiometric amount of catechol methyl borate combined with an array of radical chain processes. This simple one‐pot radical‐chain deboronative method enables the conversion of pinacol boronic esters into iodides, bromides, chlorides, and thioethers. The process is also suitable

  由空气敏感的有机硼化合物通过硼的核均热取代生成以碳为中心的自由基是生成未官能化和官能化自由基的通用方法。由于降低的路易斯酸度，烷基硼酸频哪醇酯不是合适的底物。我们报道了它们通过硼亚基酯交换与亚化学计量的邻苯二酚甲基硼酸酯结合一系列自由基链过程而原位转化为烷基硼邻苯二酚酯。这种简单的单锅自由基链脱硼方法可将频哪醇硼酸酯转化为碘化物，溴化物，氯化物和硫醚。该方法也适用于使用磺酰基自由基捕获剂通过C-C键形成腈和烯丙基化的化合物。
• Synthesis of Pyrrolidines by a Csp ³ ‐Csp ³ /Csp ³ ‐ <i>N</i> Transition‐Metal‐Free Domino Reaction of Boronic Acids with γ‐Azido‐ <i>N</i> ‐Tosylhydrazones
  作者：Lucía Florentino、Lucía López、Raquel Barroso、María‐Paz Cabal、Carlos Valdés

  DOI：10.1002/anie.202010528

  日期：2021.1.18

  The reaction between γ‐azido‐N‐tosylhydrazones and boronic acids leads to the obtention of 2,2‐disubstituted pyrrolidines in a domino process that includes 1) diazoalkane formation, 2) intermolecular carboborylation of the diazocompound, and 3) intramolecular carborylation of the azide, and comprises the formation of a Csp3−Csp3 and a Csp3−N bonds on the same carbon atom. The reaction proceeds without

  γ-叠氮基-N-甲苯磺酰hydr与硼酸之间的反应导致在多米诺骨牌过程中获得2,2-二取代的吡咯烷，包括1）重氮烷的形成，2）重氮化合物的分子间碳基化和3）分子内碳基化叠氮化物，并且包括在同一碳原子上形成Csp 3 -Csp 3和Csp 3 -N键。该反应在微波活化下无需任何过渡金属催化剂即可进行，并且在两个反应伙伴中均具有广泛的作用范围。它可以同等效率应用于烷基和芳基硼酸。与N衍生自2-（2-叠氮基乙基）-环戊酮和环己酮的-甲苯磺酰hydr反应的非对映选择性很高，导致顺式稠合双环系统成为独特的非对映异构体。超过60个示例说明了该过程的范围，包括天然生物碱中存在的支架，并且基于DFT的计算支持了该机制建议。
• sp²−sp³ Hybridized Mixed Diboron: Synthesis, Characterization, and Copper-Catalyzed β-Boration of α,β-Unsaturated Conjugated Compounds
  作者：Ming Gao、Steven B. Thorpe、Webster L. Santos

  DOI：10.1021/ol901359n

  日期：2009.8.6

  A novel sp2−sp3 hybridized mixed diboron and its reactivity on the copper-catalyzed β-boration of α,β-unsaturated conjugated compounds to afford the corresponding β-borated compounds is reported. The presence of sp3-hybridized boron provides a mild β-boration condition in the absence of phosphine and base additives. Finally, our investigations demonstrate that the sp2-hybridized boron of the mixed

  报道了一种新颖的sp 2 -sp 3杂交的混合二硼及其在α，β-不饱和共轭化合物的铜催化的β-硼酸酯上的反应性，从而提供了相应的β-硼酸酯化的化合物。sp 3-杂化硼的存在在没有膦和碱添加剂的情况下提供了温和的β-硼化条件。最后，我们的研究表明混合二硼的sp 2-杂化硼被选择性转移到共轭底物的β-碳上。
• Addition and Coupling Reactions of Bis(pinacolato)diboron Mediated by CuCl in the Presence of Potassium Acetate
  作者：Kou Takahashi、Tatsuo Ishiyama、Norio Miyaura

  DOI：10.1246/cl.2000.982

  日期：2000.9

  The addition of bis(pinacolato)diboron [(Me4C2O2)B-B(O2C2Me4)] to α,β-unsaturated ketones, esters, nitriles, or terminal alkynes and the coupling with allyl chlorides were carried out in DMF at room temperature in the presence of CuCl and AcOK. The transmetalation from boron to copper generating a B–Cu species was proposed as the key step of the reactions.

  将双(频哪醇)二硼[(Me4C2O2)B-B(O2C2Me4)]加入α,β-不饱和酮、酯、腈或末端炔烃，并与烯丙基氯在DMF中于室温下进行偶联反应，反应体系中存在CuCl和AcOK。从硼到铜的转金属化生成B–Cu物种被认为是反应的关键步骤。
• Tandem β-Boration/Arylation of α,β-Unsaturated Carbonyl Compounds by Using a Single Palladium Complex To Catalyse Both Steps
  作者：Amadeu Bonet、Henrik Gulyás、Igor O. Koshevoy、Francisco Estevan、Mercedes Sanaú、M. Angeles Úbeda、Elena Fernández

  DOI：10.1002/chem.200903095

  日期：——

  Diphenyl(3‐methyl‐2‐indolyl)phosphine (C9H8NPPh2, 1) gives stable dimeric palladium(II) complexes that contain the phosphine in P,N‐bridging coordination mode. On treating 1 with [Pd(O2CCH3)2], the new complexes [Pd(μ‐C9H7NPPh2)(NCCH3)]2 (2) or [Pd(μ‐C9H7NPPh2)(μ‐O2CCH3)]2 (3) were isolated, depending on the solvent used, acetonitrile or toluene, respectively. Further reaction of 3 with the ammonium

  二苯基（3-甲基-2-吲哚基）膦（C 9 ħ 8 NPPh 2，1包含在P中的膦）给出稳定二聚体钯（II）络合物，N-桥接配位模式。上处理1与[钯（O 2 CCH 3）2 ]，新的配合物[钯（μ-C 9 H ^ 7 NPPh 2）（NCCH 3）] 2（2）或[钯（μ-C 9 H ^ 7 NPPh 2）（μ-O 2 CCH 3）] 2（3分别根据所用溶剂，乙腈或甲苯进行分离。进一步反应3与铵盐1导致一个羧酸酯配体的替代，得到[钯（μ-C 9 H ^ 7 NPPh 2）3（μ-O 2 CCH 3）]（4），其中，所述双金属单元通过三个C键合的9 ħ 7 NPPh 2 -基团和一个羧酸基团。使用这种方法，[钯2（μ-C 6 H ^ 4 PPH 2）2（μ-C 9ħ 7 NPPh 2）（μ-O 2 CCX 3）]（X = H（7）; X = F（8））得自合成的邻-metalated化合物[钯（C