环己酮-3-硼酸酯 | 302577-72-6

• 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: 环己酮-3-硼酸酯
• 中文别名: 3-环己酮硼酸酯
• 英文名称: 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohexan-1-one
• 英文别名: 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-cyclohexanone；3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)cyclohexanone；3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohexanone；O(C6H9)(pinacolatoboron)；C6H9(O)(Bpin)；O(C6H9)Bpin；3-(Tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohexan-1-one
• CAS: 302577-72-6
• 化学式: C₁₂H₂₁BO₃
• 分子量: 224.108
• InChiKey: RDLPCDXZYPJXPO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.59
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2934999090

SDS

Material Safety Data Sheet

---

Section 1. Identification of the substance
Product Name: 3-(Tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohexan-1-one
Synonyms:

---

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

---

Section 3. Composition/information on ingredients.
Ingredient name: 3-(Tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohexan-1-one
CAS number: 302577-72-6

---

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: C12H21BO3
Molecular weight: 224.1

---

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

---

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：

  环己酮-3-硼酸酯 在 sodium perborate tetrahydrate 作用下， 反应 4.0h， 生成 3-羟基环己烷-1-酮
  参考文献：
  名称：

  手性铜（II）催化的对映选择性硼与水中α，β-不饱和羰基化合物的共轭加成反应

  摘要：

  硼上的铜销：在水中有催化量的Cu（OH）2和手性2,2'-联吡啶配体存在的情况下，对硼向α，β-不饱和化合物的1,4-对映选择性加成反应顺利进行。已显示出广泛的α，β-不饱和羰基化合物的底物范围，包括无环，环状和β，β-二取代的烯酮，α，β-不饱和酯，酰胺和腈。

  DOI：

  10.1002/anie.201207343
• 作为产物：
  描述：

  2-环己烯-1-酮 、 联硼酸频那醇酯 在 Cs₂CO₃ 、 MeOH 、 catalyst: PPh₃ 作用下， 以 四氢呋喃 为溶剂， 以84%的产率得到环己酮-3-硼酸酯
  参考文献：
  名称：

  α，β-不饱和化合物的β位置的无金属催化硼酸化：具有挑战性的不对称诱导

  摘要：

  使用史无前例的有机催化体系制备了含有β-羰基官能团的对映体富集的仲有机硼酸酯（参见方案）。在不存在过渡金属的情况下，使用手性叔磷化合物可导致ee值高达95％。

  DOI：

  10.1002/anie.201001198

文献信息

• β-Borylation of conjugated carbonyl compounds with silylborane or bis(pinacolato)diboron catalyzed by Au nanoparticles
  作者：Marios Kidonakis、Michael Fragkiadakis、Manolis Stratakis

  DOI：10.1039/d0ob01806f

  日期：——

  Conjugated aldehydes and ketones undergo reaction with Me2PhSiBpin (pin: pinacolato) catalyzed by Au nanoparticles supported on TiO2 forming exclusively the β-borylation products, via the intermediate formation of the labile silaboration adducts. This chemoselectivity pathway is complementary to the so far known analogous reaction catalyzed by other metals, where β-silylation occurs instead. β-Borylation

  共轭醛和酮与Me 2 PhSiBpin（pin：pinacolato）发生反应，这是通过不稳定形成的硅烷化加合物的中间形成，而Au纳米颗粒负载在TiO 2上，仅形成β-硼化产物。这种化学选择性途径是迄今为止由其他金属催化的类似反应的补充，在其他类似反应中发生了β-甲硅烷基化。在相同的反应条件下，在各种共轭羰基化合物中，pinBBpin也会发生β-硼化反应，这些共轭羰基化合物包括在其尝试的Au催化的合成中没有反应性的酯和酰胺。
• Impregnated Copper on Magnetite as Recyclable Catalyst for the Addition of Alkoxy Diboron Reagents to C−C Double Bonds
  作者：Rafael Cano、Diego J. Ramón、Miguel Yus

  DOI：10.1021/jo100325e

  日期：2010.5.21

  A simple protocol for the borylation with use of impregnated copper on magnetite is described. The reactions showed a very broad scope and all type of olefins could be used with similar results. The catalyst could be easily removed by a magnet and it could be reused several times, showing similar activity.

  描述了在磁铁矿上使用浸渍铜进行硼化的简单方案。反应显示出非常广泛的范围，并且可以使用所有类型的烯烃而获得相似的结果。该催化剂可以很容易地被磁铁除去，并且可以重复使用多次，表现出相似的活性。
• An NHC-CuCl functionalized metal–organic framework for catalyzing β-boration of α,β-unsaturated carbonyl compounds
  作者：Qingxia Yao、Xiufang Lu、Kaili Liu、Chao Ma、Jie Su、Cong Lin、Dacheng Li、Jianmin Dou、Junliang Sun、Wenzeng Duan

  DOI：10.1039/c9dt00645a

  日期：——

  functionalized with in situ generated NHC-CuCl units (1) has been successfully synthesized from a novel imidazolium-containing ligand. In particular, the MOF 1 can catalyze β-boration of α,β-unsaturated carbonyl compounds, while the isoreticular version of 1 (1-im) modified with only imidazolium moiety cannot. This work demonstrates for the first time the heterogeneous catalysis of NHC-Cu(I)Cl within a

  利用新型的含咪唑配体成功合成了用原位生成的NHC-CuCl单元功能化的微孔金属有机骨架（1）。尤其是，MOF 1可以催化α，β-不饱和羰基化合物的β-硼酸酯化，而仅用咪唑鎓部分修饰的1（1-im）的同质网形式则不能。这项工作首次证明了MOF固体中NHC-Cu（I）Cl的非均相催化。
• Catalytic 1,3-Difunctionalisation of Organic Backbones through a Highly Stereoselective, One-Pot, Boron Conjugate-Addition/Reduction/Oxidation Process
  作者：Cristina Solé、Amolak Tatla、Jose A. Mata、Andrew Whiting、Henrik Gulyás、Elena Fernández

  DOI：10.1002/chem.201102081

  日期：2011.12.9

  enantioselectivity provided by the CuI catalyst modified with Josiphos‐ and Mandyphos‐type ligands has been examined. The oxidative substitution of the boryl unit with a hydroxyl group proceeds with complete retention of configuration at the Cβ‐atom. In parallel, the stoichiometric reduction of the imino or carbonyl group provides a second stereogenic centre. Depending on the nature of the reducing reagent

  建立了简单的一锅三步合成路线，制备手性1,3-氨基醇和1,3-二醇。考虑到合成方案的整体立体控制，第一步和关键步骤分别是对映选择性的α，β-不饱和亚胺和酮的β-硼酸酯。研究了用Josiphos和Mandyphos型配体改性的Cu I催化剂提供的对映选择性。的甲硼烷基单元的氧化性取代与在C配置的完全保留的羟基进行β -原子。同时，亚氨基或羰基的化学计量还原提供了第二个立体定向中心。根据还原剂的性质，可以实现极高的非对映选择性，特别是对于合成试剂而言。-1,3-氨基醇和1,3-二醇
• Organocatalytic versus Iron-Assisted β-Boration of Electron-Deficient Olefins
  作者：Amadeu Bonet、Cristina Sole、Henrik Gulyás、Elena Fernández

  DOI：10.1002/asia.201000826

  日期：2011.4.4

  Combo effects: The first example of an iron‐mediated β‐boration of activated olefins is reported. The origin and the benefits of the catalytic activity associated with the presence of iron have been questioned and carefully studied. The iron system has been compared to the organocatalytic β‐boration of α,β‐unsaturated esters, ketones, and imines (see scheme; acac=acetylacetonate, pin=pinacol).

  组合效应：报道了铁介导的活化烯烃的β-硼酸酯化的第一个例子。与铁的存在有关的催化活性的起源和益处已受到质疑和仔细研究。已将铁系统与α，β-不饱和酯，酮和亚胺的有机催化β-硼酸酯（参见方案； acac =乙酰丙酮酸酯，pin =频哪醇）进行了比较。