(1R,5S)-(+)-2-氧杂二环[3.3.0]辛-6-烯-3-酮 | 54483-22-6

• 物质功能分类: 有机原料 - 酮类化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 中文名称: (1R,5S)-(+)-2-氧杂二环[3.3.0]辛-6-烯-3-酮
• 中文别名: (1R,5S)-(+)-2-氧杂双环[3.3.0]辛-6-烯-3-酮
• 英文名称: (1R,5S)-2-oxabicyclo[3.3.0]oct-6-en-3-one
• 英文别名: (1R,5S)-2-oxabicyclo<3.3.0>oct-6-en-3-one；(3aS,6aR)-3,3a,6,6a-tetrahydro-2H-cyclopenta[b]furan-2-one；cis-3,3a,6,6a-tetrahydro-2H-cyclopenta(b)furan-2-one；(3aS,6aR)-3,3a,6,6a-tetrahydrocyclopenta[b]furan-2-one
• CAS: 54483-22-6
• 化学式: C₇H₈O₂
• 分子量: 124.139
• InChiKey: RYBPGUMSFWGGLP-PHDIDXHHSA-N

物化性质

• 熔点：
  45-48 °C(lit.)
• 沸点：
  190.92°C (rough estimate)
• 密度：
  1.1006 (rough estimate)
• 闪点：
  >230 °F
• 稳定性/保质期：
  遵循规定使用和储存，则不会发生分解。

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 安全说明：
  S22,S24/25
• 海关编码：
  2932209090
• 储存条件：
  存储于0至6℃的阴凉干燥处。

SDS

Name:	(+)-Cis-2-Oxabicyclo(3.3.0)Oct-6-En-3-One 97% Material Safety Data Sheet
Synonym:	(+)-3-3A,6,6A-Tetrahydro-sH-Cyclopenta(b)Furan-2-one
CAS:	54483-22-6

Section 1 - Chemical Product MSDS Name:(+)-Cis-2-Oxabicyclo(3.3.0)Oct-6-En-3-One 97% Material Safety Data Sheet
Synonym:(+)-3-3A,6,6A-Tetrahydro-sH-Cyclopenta(b)Furan-2-one

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
54483-22-6	(+)-Cis-2-Oxabicyclo(3.3.0)Oct-6-En-3-	97%	unlisted

Hazard Symbols: None Listed.
Risk Phrases: None Listed.

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
The toxicological properties of this material have not been fully investigated.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation.
Ingestion:
May cause irritation of the digestive tract. The toxicological properties of this substance have not been fully investigated.
Inhalation:
May cause respiratory tract irritation. The toxicological properties of this substance have not been fully investigated.
Chronic:
No information found.

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Section 4 - FIRST AID MEASURES
Eyes: Flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse.
Ingestion:
Never give anything by mouth to an unconscious person. Get medical aid. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water.
Inhalation:
Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.
Notes to Physician:

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Section 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Runoff from fire control or dilution water may cause pollution.
Extinguishing Media:
Use agent most appropriate to extinguish fire. Use water spray, dry chemical, carbon dioxide, or appropriate foam.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Vacuum or sweep up material and place into a suitable disposal container. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions.
Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Use with adequate ventilation. Minimize dust generation and accumulation. Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion and inhalation.
Storage:
Keep container closed when not in use. Store in a tightly closed container. Keep refrigerated. (Store below 4C/39F.)

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 54483-22-6: Personal Protective Equipment Eyes: Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to minimize contact with skin.
Respirators:
Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure limits are exceeded or if irritation or other symptoms are experienced.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Crystals
Color: slightly beige
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 46.00 - 47.00 deg C
Autoignition Temperature: Not applicable.
Flash Point: Not applicable.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C7H8O2
Molecular Weight: 124.14

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Incompatible materials, dust generation, excess heat, strong oxidants.
Incompatibilities with Other Materials:
Oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, irritating and toxic fumes and gases, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 54483-22-6 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
(+)-Cis-2-Oxabicyclo(3.3.0)Oct-6-En-3-One - Not listed by ACGIH, IARC, or NTP.

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Section 12 - ECOLOGICAL INFORMATION

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Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

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Section 14 - TRANSPORT INFORMATION

IATA
Not regulated as a hazardous material.
IMO
Not regulated as a hazardous material.
RID/ADR
Not regulated as a hazardous material.

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: Not available.
Risk Phrases:
Safety Phrases:
S 24/25 Avoid contact with skin and eyes.
WGK (Water Danger/Protection)
CAS# 54483-22-6: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 54483-22-6 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 54483-22-6 is not listed on the TSCA inventory.
It is for research and development use only.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

用于合成碳环核苷的关键结构单元。

反应信息

• 作为反应物：
  描述：

  (1R,5S)-(+)-2-氧杂二环[3.3.0]辛-6-烯-3-酮 在 吡啶 、 六甲基磷酰三胺 、 sodium hydroxide 、 potassium triiodide 、 三正丁基氢锡 作用下， 以 乙酸乙酯 为溶剂， 反应 76.0h， 生成 前列腺素中间体
  参考文献：
  名称：

  Ishizuka, Naoyasu; Miyamura, Souji; Takeuchi, Tadashi, Heterocycles, 1980, vol. 14, # 8, p. 1123 - 1124

  摘要：

  DOI：
• 作为产物：
  描述：

  1,6-庚二烯-4-醇 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 4-二甲氨基吡啶 、 lithium hydroxide 、 dirhodium(II) tetrakis[methyl 4(R)-1-(3-phenylpropanoyl)-2-imidazolidinone-4-carboxylate] 、 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 20.5h， 生成 (1R,5S)-(+)-2-氧杂二环[3.3.0]辛-6-烯-3-酮
  参考文献：
  名称：

  手性氨基甲酸酯（II）分子内插入碳氢氢短时立体选择性合成（+）-和（-）-2-氧杂双环[3.3.0] oct-6-en-3-one

  摘要：

  （1 S，5 R）-（-）-2-氧杂双环[3.3.0] oct-6-en-3-one的合成，是从二乙烯基甲醇通过催化复分解和C到各种前列腺素的有用合成前体。描述了3-环戊烯基重氮乙酸酯的H插入。在插入过程中已达到90±1％的对映选择性。

  DOI：

  10.1016/s0957-4166(03)00083-1

文献信息

• Discovery of Baeyer–Villiger monooxygenases from photosynthetic eukaryotes
  作者：Elisa Beneventi、Mattia Niero、Riccardo Motterle、Marco Fraaije、Elisabetta Bergantino

  DOI：10.1016/j.molcatb.2013.10.006

  日期：2013.12

  Baeyer–Villiger monooxygenases are attractive “green” catalysts able to produce chiral esters or lactones starting from ketones. They can act as natural equivalents of peroxyacids that are the catalysts classically used in the organic synthesis reactions, consisting in the cleavage of CC bonds with the concomitant insertion of an oxygen atom.

  拜耳－维利格单加氧酶是有吸引力的“绿色”催化剂，能够从酮开始生产手性酯或内酯。它们可以充当过氧酸的天然等同物，过氧酸是有机合成反应中传统使用的催化剂，包括CC键的断裂和氧原子的同时插入。
• Genome mining reveals new bacterial type I Baeyer-Villiger monooxygenases with (bio)synthetic potential
  作者：Romina D. Ceccoli、Dario A. Bianchi、María Ayelén Carabajal、Daniela V. Rial

  DOI：10.1016/j.mcat.2020.110875

  日期：2020.5

  monooxygenases (BVMOs) are oxidorreductases that catalyze the oxidation of ketones in a very selective manner. By genome mining we detected seven putative type I BVMOs in Bradyrhizobium diazoefficiens USDA 110. As we established the phylogenetic relationships among them and with other type I BVMOs, we found out that they belong to different clades of the phylogenetic tree. Thus, we decided to clone and

  摘要 Baeyer-Villiger 单加氧酶 (BVMOs) 是一种氧化还原酶，以非常选择性的方式催化酮的氧化。通过基因组挖掘，我们在重氮慢生根瘤菌 USDA 110 中检测到了七个推定的 I 型 BVMO。当我们建立它们之间以及与其他 I 型 BVMO 的系统发育关系时，我们发现它们属于系统发育树的不同进化枝。因此，我们决定克隆并异源表达其中的五个。其中三个，每个来自不同的系统发育组，作为可溶性蛋白质获得，使我们能够继续进行它们的生物催化评估和酶学表征。至于底物范围和选择性，我们观察到三种 BVMO 之间的互补行为。
• Characterization and Crystal Structure of a Robust Cyclohexanone Monooxygenase
  作者：Elvira Romero、J. Rubén Gómez Castellanos、Andrea Mattevi、Marco W. Fraaije

  DOI：10.1002/anie.201608951

  日期：2016.12.19

  Cyclohexanone monooxygenase (CHMO) is a promising biocatalyst for industrial reactions owing to its broad substrate spectrum and excellent regio-, chemo-, and enantioselectivity. However, the low stability of many Baeyer-Villiger monooxygenases is an obstacle for their exploitation in industry. Characterization and crystal structure determination of a robust CHMO from Thermocrispum municipale is reported

  环己酮单加氧酶（CHMO）由于其广泛的底物谱以及出色的区域，化学和对映选择性而成为一种有希望的工业反应生物催化剂。然而，许多Baeyer-Villiger单加氧酶的低稳定性是其在工业中开发的障碍。报道了来自Thermocrispum Municipale的稳健的CHMO的表征和晶体结构测定。该酶可以有效地转化各种脂肪族，芳香族和环状酮类以及前手性硫化物。紧凑的基片装订腔解释了它偏爱小而不是笨重的基片。用纯化的酶或全细胞进行的小规模转化证明了这种新发现的CHMO的显着特性。
• Chiral aluminum complexes as catalysts in asymmetric Baeyer-Villiger reactions of cyclobutanones
  作者：Carsten Bolm、Oliver Beckmann、Chiara Palazzi

  DOI：10.1139/v01-137

  日期：2001.11.1

  employed as mediators and catalysts in asymmetric Baeyer-Villiger rearrangements of cyclobutanones. Good enantioselectivies were achieved with only 15 mol% of the chosen chiral Lewis acid. The enantiomeric excesses obtained have never been reached before in such metal-catalyzed Baeyer-Villiger reactions.Key words: aluminum, asymmetric catalysis, lactones, oxidations, rearrangement.

  BINOL-铝配合物成功地用作环丁酮不对称拜尔-维利格重排的介体和催化剂。仅使用 15 mol% 所选手性路易斯酸即可获得良好的对映选择性。在这种金属催化的 Baeyer-Villiger 反应中，获得的对映体过量以前从未达到过。关键词：铝，不对称催化，内酯，氧化，重排。
• Catalytic Asymmetric Baeyer-Villiger Oxidation in Water by Using Pt^IICatalysts and Hydrogen Peroxide: Supramolecular Control of Enantioselectivity
  作者：Alessandra Cavarzan、Giulio Bianchini、Paolo Sgarbossa、Laurent Lefort、Serafino Gladiali、Alessandro Scarso、Giorgio Strukul

  DOI：10.1002/chem.200900294

  日期：2009.8.10

  chiral cyclobutanones 7 and 10: with 7 the best catalyst was 1 g, whereas with the larger substrate, 10, complexes 1 a–b performed better in terms of enantioselectivity. Each combination of substrate, catalyst and surfactant is a new system and supramolecular reciprocal interactions together with the hydrophobic character of the counterparts play crucial roles. The asymmetric Baeyer–Villiger oxidation

  环酮的对映选择性 Baeyer-Villiger 氧化是一个具有挑战性的反应，尤其是在使用环保氧化剂时。通过使用软路易斯酸 Pt II在水中进行反应具有手性二膦和单膦的配合物。添加表面活性剂是至关重要的，它会导致形成充当纳米反应器的胶束，其中底物和催化剂在有序介质中相互接触，在某些情况下，这会对反应的转化率和选择性产生积极影响。这是由于疏水效应（将反应组分限制在胶束中）以及表面活性剂的烷基链提供的有序栅栏内的伙伴之间的超分子相互作用的组合。对于内消旋环丁酮的氧化，添加表面活性剂使反应以高产率和对映体过量（ee; 56 %) 高于有机溶剂。随后对内消旋环己酮的扩展导致产率普遍下降，但对映选择性（ee高达 92%）从有机介质转移到水-表面活性剂介质，无论使用何种底物或催化剂。使用手性环丁酮7和10观察到不同的行为：使用7时最好的催化剂是1 g，而使用较大的底物10时，配合物1 a – b在对映