1,5-脱水-2-脱氧-6-O-(苯基甲基)-D-阿拉伯-己-1-烯糖 | 165524-85-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1,5-脱水-2-脱氧-6-O-(苯基甲基)-D-阿拉伯-己-1-烯糖
• 英文名称: 6-O-(benzyl)-D-glucal
• 英文别名: 6-O-benzyl-D-glucal；6-benzylglucal；(2R,3S,4R)-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran-3,4-diol
• CAS: 165524-85-6
• 化学式: C₁₃H₁₆O₄
• 分子量: 236.268
• InChiKey: RHDGBCAJRWMYHR-UPJWGTAASA-N

物化性质

• 沸点：
  384.1±42.0 °C(Predicted)
• 密度：
  1.247±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

安全信息

• 安全说明：
  S24/25

SDS

Name:	6-O-Benzyl-D-glucal Material Safety Data Sheet
Synonym:
CAS:	165524-85-6

Section 1 - Chemical Product MSDS Name:6-O-Benzyl-D-glucal Material Safety Data Sheet
Synonym:

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
165524-85-6	6-O-Benzyl-D-glucal		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:
Absorb spill with inert material (e.g. vermiculite, sand or earth), then place in suitable container. 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# 165524-85-6: 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 or liquid
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: C13H16O4
Molecular Weight: 236.27

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

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 165524-85-6 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
6-O-Benzyl-D-glucal - 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
Shipping Name: Not regulated.
Hazard Class:
UN Number:
Packing Group:
IMO
Shipping Name: Not regulated.
Hazard Class:
UN Number:
Packing Group:
RID/ADR
Shipping Name: Not regulated.
Hazard Class:
UN Number:
Packing group:

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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# 165524-85-6: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 165524-85-6 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 165524-85-6 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

反应信息

• 作为反应物：
  描述：

  1,5-脱水-2-脱氧-6-O-(苯基甲基)-D-阿拉伯-己-1-烯糖 在 吡啶 、 咪唑 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 生成 6-O-(benzyl)-4-O-mesyl-D-glucal
  参考文献：
  名称：

  O-，S-，N-和C-亲核试剂与衍生自d-Glucal的β乙烯基环氧乙烷的区域和立体选择性

  摘要：

  在与O-，C-，N-和S-亲核试剂的加成反应中，研究了衍生自d-葡糖醛的6- O -Trity1-（1a）和6-（O-苄基）-取代的环氧化物（1b）。通常根据亲核体与环氧乙烷氧配位的能力观察到1，4-区域和β-立体选择性或抗1，2-加成途径。当将TMSN 3或LiN 3用作基于叠氮化物的亲核试剂时，还会观察到1,2-syn加成途径。

  DOI：

  10.1021/jo048981b
• 作为产物：
  描述：

  乙酰化葡萄烯糖 在 甲醇 、 sodium methylate 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 11.0h， 生成 1,5-脱水-2-脱氧-6-O-(苯基甲基)-D-阿拉伯-己-1-烯糖
  参考文献：
  名称：

  通过将有机锂试剂未催化的1,4-加成到糖基衍生的乙烯基环氧乙烷上而实现的新的立体选择性β-C-糖基化。

  摘要：

  [反应：请参见文本]环氧4是由d-葡萄糖衍生的羟基甲磺酸酯3原位生成的。环氧4与一系列烷基锂和芳基锂试剂反应生成2,3-不饱和的β-C-糖苷，具有优异的1， β-糖苷的4-区域选择性和完全立体选择性。其他有机金属试剂在与环氧化物4的反应中表现出更复杂的行为。

  DOI：

  10.1021/ol034662f

文献信息

• A 3,4-<i>trans</i>-Fused Cyclic Protecting Group Facilitates α-Selective Catalytic Synthesis of 2-Deoxyglycosides
  作者：Edward I. Balmond、David Benito-Alifonso、Diane M. Coe、Roger W. Alder、Eoghan M. McGarrigle、M. Carmen Galan

  DOI：10.1002/anie.201403543

  日期：2014.7.28

  disaccharides or glycoconjugates with high α‐selectivity and yields (77–97 %) using a trans‐fused cyclic 3,4‐O‐disiloxane protecting group and TsOH⋅H2O (1 mol %) as a catalyst. Control of the anomeric selectivity arises from conformational locking of the intermediate oxacarbenium cation. Glucals outperform rhamnals because the C6 side‐chain conformation augments the selectivity.

  已经开发出一种实用的方法，使用反式稠合环状 3,4-O-二硅氧烷保护基团和 TsOH⋅H 2 O ，将葡糖和鼠李糖转化为具有高α-选择性和产率（77-97%）的二糖或糖缀合物（ 1 mol%) 作为催化剂。异头选择性的控制来自中间氧杂碳鎓阳离子的构象锁定。Glucals 优于鼠李糖醇，因为 C6 侧链构象增强了选择性。
• Strategy in Oligosaccharide Synthesis:  An Application to a Concise Total Synthesis of the KH-1(adenocarcinoma) Antigen
  作者：Prashant P. Deshpande、Hyunjin M. Kim、Andrzej Zatorski、Tae-Kyo Park、Govindaswami Ragupathi、Philip O. Livingston、David Live、Samuel J. Danishefsky

  DOI：10.1021/ja9725864

  日期：1998.2.1

  A concise and potentially practical synthesis of the title compound has been achieved. The route features a high degree of convergence and economy of synthetic operations. A key step is the concurrent introductory addition of three α-l-fucosyl residues at required hydroxyl acceptor sites (see 37 → 39). Conjugation to carrier protein was achieved, and a route to include truncated structures for investigations

  已经实现了标题化合物的简洁且可能实用的合成。该路线具有高度的收敛性和合成操作的经济性。一个关键步骤是在所需的羟基受体位点同时引入三个 α-l-岩藻糖残基（参见 37 → 39）。实现了与载体蛋白的缀合，并完成了包括用于研究抗体特异性的截短结构的途径。
• Attempts To Improve the Overall Stereoselectivity of the Ireland−Claisen Rearrangement
  作者：Chi-Li Chen、Kosuke Namba、Yoshito Kishi

  DOI：10.1021/ol8027225

  日期：2009.1.15

  With focus on the steric effects present in the transition states for the [3,3]-sigmatropic rearrangement, the substrate 5 has been designed to improve the overall stereoselectivity of the Ireland−Claisen rearrangement. Experimentally, it has been found that (1) only Z-6 rearranges to 7 at 80 °C and (2) E-6 isomerizes to Z-6 at 80 °C, thereby allowing the transformation of 5 into 7 in an almost quantitative

  着眼于 [3,3]-σ 重排的过渡态中存在的空间效应，底物5已被设计为提高爱尔兰-克莱森重排的整体立体选择性。实验发现，(1) 只有Z -6在 80 °C 下重排为7和 (2) E -6 在 80 °C 下异构化为Z -6，从而允许5以几乎定量的方式转化为7屈服。为了说明这种方法的有用性，给出了两个额外的例子。
• The convergent total synthesis and antibacterial profile of the natural product streptothricin F
  作者：Matthew G. Dowgiallo、Brandon C. Miller、Mintesinot Kassu、Kenneth P. Smith、Andrew D. Fetigan、Jason J. Guo、James E. Kirby、Roman Manetsch

  DOI：10.1039/d1sc06445b

  日期：——

  The second ever total synthesis of streptothricin F and the first achieved through a diversity-enabling convergent route. The synthesis is achieved in 35 total steps, with a longest linear sequence of 19 steps, and 0.40% overall yield.

  第二次合成链霉素F的全合成，首次通过多样性促进的汇聚路线实现。该合成共经过35个步骤，最长线性序列为19步，总产率为0.40%。
• Cooperative Bifurcated Chalcogen Bonding and Hydrogen Bonding as Stereocontrolling Elements for Selective Strain-Release Septanosylation
  作者：Wenpeng Ma、Jan-Lukas Kirchhoff、Carsten Strohmann、Bastian Grabe、Charles C. J. Loh

  DOI：10.1021/jacs.3c06984

  日期：2023.12.13

  synthesis. In particular, there has been significant recent interest in the harnessing of unconventional NCIs to surmount difficult selectivity challenges in glycosylations. Herein, we disclose the exploitation of an unconventional bifurcated chalcogen bonding and hydrogen bonding (HB) network, which paves the way for a robust catalytic strategy into biologically useful seven-membered ring sugars. Through

  非共价相互作用（NCI）的利用正在成为解决合成中广泛的立体选择性挑战的重要手段。特别是，最近人们对利用非常规 NCI 来克服糖基化中困难的选择性挑战产生了浓厚的兴趣。在此，我们公开了一种非常规分叉硫族键合和氢键合（HB）网络的开发，这为生物上有用的七元环糖的稳健催化策略铺平了道路。通过13 C 核磁共振 (NMR) 原位监测、NMR 滴定实验和密度泛函理论 (DFT) 建模，我们提出了由分叉硫族键合机制组成的多个官能团的显着同时激活HB激活。值得注意的是，安装在糖基供体上的酯部分对于建立用于立体控制的假定三元复合物至关重要。通过13 C 动力学同位素效应和动力学研究，我们的数据证实了解离的 S N i 型机制构成了优异的 α 选择性的立体控制基础。