2,6-脱水-1,5-二脱氧-L-阿拉伯-己-5-烯糖二乙酸酯 | 54621-94-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 2,6-脱水-1,5-二脱氧-L-阿拉伯-己-5-烯糖二乙酸酯
• 英文名称: 3,4-di-O-acetyl-L-fucal
• 英文别名: di-O-acetyl-L-fucal；(2S,3R,4S)-2-methyl-3,4-dihydro-2H-pyran-3,4-diyl diacetate；3,4-diacetyl-L-fucal；(2S,3R,4S)-4-(acetyloxy)-2-methyl-3,4-dihydro-2H-pyran-3-yl acetate；[(2S,3R,4S)-3-acetyloxy-2-methyl-3,4-dihydro-2H-pyran-4-yl] acetate
• CAS: 54621-94-2
• 化学式: C₁₀H₁₄O₅
• 分子量: 214.218
• InChiKey: NDEGMKQAZZBNBB-JMOVZRAMSA-N

物化性质

• 溶解度：
  DMF：30mg/mL； DMSO：30mg/mL；乙醇：30mg/mL

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

安全信息

• 安全说明：
  S24/25
• 海关编码：
  2932999099
• 储存条件：
  室温

SDS

Name:	3 4-Di-O-acetyl-L-fucal Material Safety Data Sheet
Synonym:
CAS:	54621-94-2

Section 1 - Chemical Product MSDS Name:3 4-Di-O-acetyl-L-fucal Material Safety Data Sheet
Synonym:

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
54621-94-2	3,4-Di-O-acetyl-L-fucal		unlisted

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

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Not available.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation. May be harmful if absorbed through the skin.
Ingestion:
May cause irritation of the digestive tract. May be harmful if swallowed.
Inhalation:
May cause respiratory tract irritation. May be harmful if inhaled.
Chronic:
Not available.

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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.
Ingestion:
Get medical aid. Wash mouth out with water.
Inhalation:
Remove from exposure and move to fresh air immediately.
Notes to Physician:
Treat symptomatically and supportively.

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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.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical 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.

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Section 7 - HANDLING and STORAGE
Handling:
Avoid breathing dust, vapor, mist, or gas. Avoid contact with skin and eyes.
Storage:
Store in a cool, dry place. Store in a tightly closed container.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 54621-94-2: Personal Protective Equipment Eyes: Not available.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
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: Solid
Color: Not available.
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: Not available.
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C10H14O5
Molecular Weight: 214.22

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable.
Conditions to Avoid:
Incompatible materials.
Incompatibilities with Other Materials:
Strong oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, carbon dioxide.
Hazardous Polymerization: Will not occur.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 54621-94-2 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
3,4-Di-O-acetyl-L-fucal - 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# 54621-94-2: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 54621-94-2 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 54621-94-2 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

3,4-二-O-乙酰-L-岩藻糖是从专利WO1999026956A1中提取出的一种用于合成抗生素的反应物。

反应信息

• 作为反应物：
  描述：

  2,6-脱水-1,5-二脱氧-L-阿拉伯-己-5-烯糖二乙酸酯 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以95%的产率得到L-fucal
  参考文献：
  名称：

  Synthesis of a selective inhibitor of a fucose binding bacterial lectin from Burkholderia ambifaria

  摘要：

  安氏伯克霍尔德氏菌（Burkholderia ambifaria）是伯克霍尔德氏头孢菌素复合菌（Burkholderia cepacia complex，BCC）中的一种细菌，这是一类密切相关的革兰氏阴性菌，是免疫力低下患者 "头孢菌素综合征 "的致病菌。B. ambifaria 产生一种岩藻糖结合凝集素 BambL，这种凝集素对人类岩藻糖化表位具有很强的特异性。在这里，我们首次报道了能够在微摩尔范围内选择性结合病原体凝集素 BambL 的合成配体。我们介绍了制备α构象受限岩藻糖苷的合成路线，重点是完全非对映选择性的反电子需求[4 + 2] Diels-Alder反应。等温滴定量热法（ITC）表明，该化合物与病原体相关凝集素 BambL 的结合亲和力与天然含岩藻糖的低聚糖相当。铜绿假单胞菌的岩藻糖结合凝集素 LecB 与该化合物没有结合，而这两种凝集素之间的亲和力差异可以通过建模得到合理解释。此外，SPR 分析表明，这种岩藻糖模拟物不与人类岩藻糖结合凝集素 DC-SIGN 结合，从而支持了对 B. ambifaria 凝集素的选择性结合特征。

  DOI：

  10.1039/c3ob40520f
• 作为产物：
  描述：

  D-Fucose 在 sodium dihydrogenphosphate 、 高氯酸 、 氢溴酸 、 溶剂黄146 、 锌 作用下， 以 二氯甲烷 、 水 、 乙酸乙酯 为溶剂， 反应 4.5h， 生成 2,6-脱水-1,5-二脱氧-L-阿拉伯-己-5-烯糖二乙酸酯
  参考文献：
  名称：

  Synthesis of Staphylococcus aureus Type 5 Trisaccharide Repeating Unit: Solving the Problem of Lactamization

  摘要：

  The chemical synthesis of an orthogonally protected trisaccharide derived from the polysaccharide of Staphylococcus aureus Type 5, which is an attractive candidate for the development of immunotherapies, is described. The challenging alpha-fucosylation and beta-mannosylation are addressed through the careful choice of protecting groups. Lactamization of a beta-D-ManpNAcA moiety during deprotection was avoided by a late stage oxidation approach. Versatility of the trisaccharide was demonstrated by its transformation into a spacer-containing repeating unit suitable for immunological investigations.

  DOI：

  10.1021/acs.orglett.5b00031

文献信息

• Total Synthesis of a Densely Functionalized <i>Plesiomonas shigelloides</i> Serotype 51 Aminoglycoside Trisaccharide Antigen
  作者：Chunjun Qin、Benjamin Schumann、Xiaopeng Zou、Claney L. Pereira、Guangzong Tian、Jing Hu、Peter H. Seeberger、Jian Yin

  DOI：10.1021/jacs.8b00148

  日期：2018.2.28

  functionalized trisaccharide repeating unit 2 from P. shigelloides serotype 51 from three monosaccharides. A judicious choice of building blocks and reaction conditions allowed for the four amino groups adorning the sugar rings to be installed with two N-acetyl (Ac) groups, rare acetamidino (Am), and d-3-hydroxybutyryl (Hb) groups. The strategy for the differentiation of amino groups in trisaccharide 2 will

  Plesiomonas shigelloides 是一种导致严重旅行者腹泻频繁爆发的病原体，会导致严重的肠外感染。由于抗生素耐药性增加和疫苗不可用，由志贺氏假单胞菌引起的败血症和脑膜炎与高死亡率有关。病原体表达的碳水化合物抗原通常在结构上是独特的，是开发疫苗和诊断的目标。在这里，我们报告了来自三种单糖的志贺氏菌血清型 51 的高度功能化三糖重复单元 2 的全合成。对构建块和反应条件的明智选择允许装饰糖环的四个氨基与两个 N-乙酰 (Ac) 基团、罕见的乙酰脒基 (Am) 和 d-3-羟基丁酰基 (Hb) 基团一起安装。
• Copper Reactivity Can Be Tuned to Catalyze the Stereoselective Synthesis of 2-Deoxyglycosides from Glycals
  作者：Carlos Palo-Nieto、Abhijit Sau、Robin Jeanneret、Pierre-Adrien Payard、Aude Salamé、Maristela Braga Martins-Teixeira、Ivone Carvalho、Laurence Grimaud、M. Carmen Galan

  DOI：10.1021/acs.orglett.9b04525

  日期：2020.3.6

  We demonstrate that tuning the reactivity of Cu by the choice of oxidation state and counterion leads to the activation of both "armed" and "disarmed" type glycals toward direct glycosylation leading to the α-stereoselective synthesis of deoxyglycosides in good to excellent yields. Mechanistic studies show that CuI is essential for effective catalysis and stereocontrol and that the reaction proceeds

  我们证明，通过选择氧化态和抗衡离子来调节Cu的反应性会导致“武装”和“解除武装”型糖类朝着直接糖基化的活化，从而导致以良好的优良收率合成脱氧糖苷的α-立体选择性合成。机理研究表明，CuI对于有效催化和立体控制至关重要，并且该反应通过烯醇醚和OH亲核试剂的双重活化而进行。
• Electrophilic Fluorination−Nucleophilic Addition Reaction Mediated by Selectfluor: Mechanistic Studies and New Applications
  作者：Stéphane P. Vincent、Michael D. Burkart、Chung-Ying Tsai、Zhiyuan Zhang、Chi-Huey Wong

  DOI：10.1021/jo990686h

  日期：1999.7.1

  The electrophilic fluorination-nucleophilic addition reaction with Selectfluor-type reagents upon glycals has been studied and optimized. This reaction leads to selective fluorination at the 2-position with concomitant nucleophilic addition to the anomeric center. To understand the stereochemical outcome of this process, a mechanistic study has led to the discovery that, in the fucose series, Selectfluor

  已经研究和优化了与 Selectfluor 型试剂在糖基上的亲电氟化-亲核加成反应。该反应导致在 2 位选择性氟化，同时对异头中心进行亲核加成。为了了解该过程的立体化学结果，一项机制研究发现，在岩藻糖系列中，Selectfluor 以顺式方式特异性添加，产生 1-[TEDA-CH2Cl]-2-氟糖，该糖缓慢异构化为更稳定的中间体。研究了异头α/β分布作为反应物和条件的函数，发现保护基策略的明智选择可以提高氟化和亲核加成的立体选择性。此外，使用超敏自由基探针来探测反应，并且没有分离出自由基过程的产物特征，这表明在聚糖对 Selectfluor 的攻击期间没有发生单电子转移。还讨论了溶剂效应、Selectfluor 反离子和逐步程序的重要性。这项研究带来了产量的重要改进和更广泛的允许亲核试剂，如碳水化合物、氨基酸、磷酸盐或膦酸盐的仲醇。这一优化过程进一步应用于重要生物活性分子的修饰，包括氟化道
• TMSBr-mediated solvent- and work-up-free synthesis of α-2-deoxyglycosides from glycals
  作者：Mei-Yuan Hsu、Yi-Pei Liu、Sarah Lam、Su-Ching Lin、Cheng-Chung Wang

  DOI：10.3762/bjoc.12.164

  日期：——

  The thio-additions of glycals were efficiently promoted by a stoichiometric amount of trimethylsilyl bromide (TMSBr) to produce S-2-deoxyglycosides under solvent-free conditions in good to excellent yields. In addition, with triphenylphosphine oxide as an additive, the TMSBr-mediated direct glycosylations of glycals with a large range of alcohols were highly α-selective.

  甘露糖醛酸盐的硫加成反应可以在无溶剂条件下高效地通过等物量的溴化三甲基硅(TMSBr)催化产生良好至优异收率的S-2-脱氧糖苷。此外，加入三苯基膦氧化物作为添加剂，TMSBr介导的甘露糖醛酸盐与多种醇类的直接糖基化反应具有高度α-选择性。
• Selective deprotection of esters using magnesium and methanol
  作者：Yao-Chang Xu、Elaine Lebeau、Clint Walker

  DOI：10.1016/s0040-4039(00)73392-2

  日期：1994.8

  The use of magnesium metal in methanol for the deprotection of alkyl esters is described. This mild reagent also provides good to excellent selectivity to cleave different esters. The order of the reactivity of this reagent towards acyl cleavages was found to be: p-nitrobenzoate > acetate > benzoate > pivaloate > trifluroacetamide.

  描述了在甲醇中使用金属镁使烷基酯脱保护。这种温和的试剂还具有很好的选择性，可以裂解不同的酯。发现该试剂对酰基裂解的反应性顺序为：对硝基苯甲酸酯>乙酸酯>苯甲酸酯>新戊酸酯>三氟乙酰胺。