(4R,5R)-(-)-2,2-二甲基-ALPHA,ALPHA,ALPHA’,ALPHA’-四(1-萘基)-1,3-二恶烷-4,5-二甲醇 | 137536-94-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 中文名称: (4R,5R)-(-)-2,2-二甲基-ALPHA,ALPHA,ALPHA’,ALPHA’-四(1-萘基)-1,3-二恶烷-4,5-二甲醇
• 中文别名: （4R，5R）-（-）-2,2-二甲基-α，α，α''，α''-四（1-萘基）-1,3-二氧戊环-4,5-二甲醇；(4R,5R)-(-)-2,2-二甲基-alpha,alpha,alpha',alpha'-四(1-萘基)-1,3-二恶烷-4,5-二甲醇；(4R,5R)-(-)-2,2-二甲基-ALPHA,ALPHA,ALPHA',ALPHA'-四(1-萘基)-1,3-二恶烷-4,5-二甲醇
• 英文名称: ((4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(di(naphthalen-1-yl)methanol)
• 英文别名: [(4R,5R)-5-[hydroxy(dinaphthalen-1-yl)methyl]-2,2-dimethyl-1,3-dioxolan-4-yl]-dinaphthalen-1-ylmethanol
• CAS: 137536-94-8
• 化学式: C₄₇H₃₈O₄
• 分子量: 666.816
• InChiKey: WTZVNZRNIOJACO-NDOUMJCMSA-N

物化性质

• 熔点：
  200 °C (dec.)(lit.)
• 比旋光度：
  -290° (c 1, CH3COOC2H5)
• 密度：
  1.269±0.06 g/cm3(Predicted)
• 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)：
  10.2
• 重原子数：
  51
• 可旋转键数：
  6
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

安全信息

• 安全说明：
  S26,S36/37/39
• 危险类别码：
  R36/37/38
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  存于阴凉干燥处

SDS

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Section 1: Product Identification
(4R,5R)-(-)-2,2-Dimethyl-alpha,alpha,alpha',alpha'-tetra(1-naphthyl)-1,3-dioxolane-4,5-dimethanol, min. 97%
Chemical Name:
(R,R)-1-Nph-TADDOL
CAS Registry Number: 137536-94-8
Formula: C47H38O4
EINECS Number: none
Chemical Family: organic alcohol
Synonym: [5-(Hydroxy-di-naphthalen-1-yl-methyl)-2,2-dimethyl-[1,3]dioxolan-4-yl]-di-naphthalen-1-yl-methanol

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 137536-94-8 100% no data no data

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Section 3: Hazards Identification
Emergency Overview: Irritating to skin and eyes. Dust is irritating to respiratory tract.May be harmful if swallowed.
Primary Routes of Exposure: Ingestion ,inhalation of dust, skin, eyes
Eye Contact: Causes slight to mild irritation of the eyes.
Skin Contact: Causes slight to mild irritation of the skin.
Inhalation: Irritating to the nose, mucous membranes and respiratory tract.
Ingestion: No information available on the physiological effects of ingestion.
Acute Health Affects: Irritating to skin, eyes and respiratory tract.
Chronic Health Affects: No information available on the long-term chronic effects.
NTP: No
IARC: No
OSHA: No

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SECTION 4: First Aid Measures
Immediately flush the eyes with copious amounts of water for at least 10-15 minutes. A victim may need
Eye Exposure:
assistance in keeping their eye lids open. Get immediate medical attention.
Wash the affected area immediately with water. Remove contaminated clothing if necessary. Seek medical
Skin Exposure:
assistance if irritation persists.
Remove the victim to fresh air. Closely monitor the victim for signs of respiratory problems, such as difficulty
Inhalation:
in breathing, coughing, wheezing, or pain. In such cases seek immediate medical assistance.
Seek medical attention immediately. Keep the victim calm. Give the victim water (only if conscious). Induce
Ingestion:
vomiting only if directed by medical personnel.

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SECTION 5: Fire Fighting Measures
Flash Point: not applicable
Autoignition Temperature: none
Explosion Limits: none
Extinguishing Medium: carbon dioxide, dry powder or foam
If this product is involved in a fire, fire fighters should be equipped with a NIOSH approved positive pressure
Special Fire Fighting Procedures:
self- contained breathing apparatus and full protective clothing.
Hazardous Combustion and If involved in a fire this material may emit toxic organic fumes, carbon monoxide and carbon dioxide.
Decomposion Products:
Unusual Fire or Explosion Hazards: No unusual fire or explosion hazards.

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SECTION 6: Accidental Release Measures
Spill and Leak Procedures: Small spills can be mixed with vermiculite or sodium carbonate and swept up.

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SECTION 7: Handling and Storage
Handling and Storage: Store the material in a tightly sealed container in a cool, dry place.

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SECTION 8: Exposure Controls and Personal Protection
Eye Protection: Always wear approved safety glasses when handling a chemical substance in the laboratory.
Skin Protection: Wear protective clothing and gloves. Consult with glove manufacturer to determine the proper type of glove.
Ventilation: Handle the material in an efficient fume hood.
If ventilation is not available a respirator should be worn. The use of respirators requires a Respirator
Respirator:
Protection Program to be in compliance with 29 CFR 1910.134.
Ventilation: Handle the material in an efficient fume hood.
Additional Protection: No additional protection required.

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SECTION 9: Physical and Chemical Properties
Color and Form: white powder
Molecular Weight: 666.82
Melting Point: 200°(dec)
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: none
Solubility in Water: soluble

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SECTION 10: Stability and Reactivity
Stability: air and moisture stable solid
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: none
Incompatibility: oxidizing agents and halogens
Decomposition Products: carbon monoxide, carbon dioxide and organic fumes

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SECTION 11: Toxicological Information
RTECS Data: No information available in the RTECS files.
Carcinogenic Effects: no data
Mutagenic Effects: no data
Tetratogenic Effects: no data

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SECTION 12: Ecological Information
Ecological Information: No information available

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SECTION 13: Disposal Considerations
Disposal: Dispose of according to federal, state, and local regulations.

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SECTION 14: Transportation
Shipping Name (CFR): Non-hazardous
Hazard Class (CFR): NA
Additional Hazard Class (CFR): NA
Packaging Group (CFR): NA
UN ID Number (CFR): NA
Shipping Name (IATA): Non-hazardous
Hazard Class (IATA): NA
Additional Hazard Class (IATA): NA
Packaging Group (IATA): NA
UN ID Number (IATA): NA

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SECTION 15: Regulatory Information
TSCA: Not listed in the TSCA inventory.
SARA (Title 313): Title compound not listed.
Second Ingredient: none

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  (4R,5R)-(-)-2,2-二甲基-ALPHA,ALPHA,ALPHA’,ALPHA’-四(1-萘基)-1,3-二恶烷-4,5-二甲醇 在 三乙胺 、 三氯化磷 作用下， 以 二氯甲烷 为溶剂， 生成 [(1S,2R)-2-((3aR,8aR)-2,2-Dimethyl-4,4,8,8-tetra-naphthalen-1-yl-tetrahydro-[1,3]dioxolo[4,5-e][1,3,2]dioxaphosphepin-6-yloxy)-1-methyl-2-phenyl-ethyl]-dimethyl-amine
  参考文献：
  名称：

  New Catalysts for the Asymmetric Hydrosilylation of Ketones Discovered by Mass Spectrometry Screening

  摘要：

  A method for determining enantiomeric excess by mass spectrometry was employed to screen a family of chiral phosphite P,N-ligands for activity in the rhodium-catalyzed asymmetric hydro-silylation of ketones. The identification of an effective set of ligands was followed by preliminary studies of the reaction scope and mechanism. Asymmetric induction of 84-88% ee for larger-scale reactions was observed, which is close to the level of the best alternative catalysts previously discovered. The screening method was shown to be applicable to a variety of substrates without the need for special optimization.

  DOI：

  10.1021/jo026365e
• 作为产物：
  描述：

  1-溴代萘 、 (4R,5R)-4,5-二乙氧基羰基-2,2-二甲基二氧 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以50%的产率得到(4R,5R)-(-)-2,2-二甲基-ALPHA,ALPHA,ALPHA’,ALPHA’-四(1-萘基)-1,3-二恶烷-4,5-二甲醇
  参考文献：
  名称：

  氢键活化对Brassard's二烯与醛之间的杂Diels-Alder反应的对映选择性催化：（S）-（+）-dihydrokawain的一步合成。

  摘要：

  通过使用TADDOL衍生物作为催化剂的氢键活化反应，实现了Brassard的二烯与醛之间的第一个催化对映选择性杂Diels-Alder反应，以中等至良好的收率和高对映选择性（高达91％ee）。反应可以在无溶剂条件下或在甲苯中进行。根据产物的绝对构型和TADDOL（α，α，α'，α'-四芳基-1,3-二氧戊环-4,5-二甲醇）与羰基之间的氢键相互作用模式X射线衍射分析，提出了一种可能的催化反应机理。为了证明该方法的有效性，我们使用了天然产物（S）-（+）-二氢卡哇因，通过使用这种方法，还可以以3-苯基丙醛为原料，以50％的分离产率和69％的对映选择性一步制备。因此，该催化体系是构建δ-内酯单元的最直接方法之一，这将使该方法对于合成多种生物学上重要的化合物和天然产物非常有吸引力。

  DOI：

  10.1002/chem.200400515
• 作为试剂：
  描述：

  (Z)-(2-(1-cyclohexenyl)-ethen-1-yl)(trineophyl)stannane 、 对苯醌 在 (4R,5R)-(-)-2,2-二甲基-ALPHA,ALPHA,ALPHA’,ALPHA’-四(1-萘基)-1,3-二恶烷-4,5-二甲醇 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以100%的产率得到8-trineophylstannyltricyclo[8.4.0.0^2,7]tetradeca-4,9-diene-3,6-dione
  参考文献：
  名称：

  高效不对称TADDOLs-有机催化的环加成反应制备烯丙基锡衍生物

  摘要：

  我们在这里报告在有机催化不对称Diels-Alder反应研究中获得的结果，该反应使用（Z）-2-（1-环己烯基）-1-乙烯基（三聚氰胺）锡烷（1）作为二烯来优化立体定义的烯丙基锡衍生物的合成（4R，5R）-α，α，α'，α'-四苯基-1,3-二氧戊环-4,5-二甲醇（TADDOL，I）和类似物（4R，5R）-α存在下的取代的亲二烯体，α，α'，α'-四（1-萘基）-1,3-二氧戊环-4,5-二甲醇（II）和（4R，5R）-α，α，α'，α'-四（9） -苯菲基）1,3-二氧戊环-4,5-二甲醇（III）作为手性催化剂，通过亲二烯体的氢键活化来增强立体选择性。催化剂二 提供了优异的结果，低温下的超声波辐射显示出更短的反应时间。

  DOI：

  10.1016/j.catcom.2014.09.015

文献信息

• An organocatalyst bound α-aminoalkyl radical intermediate for controlled aerobic oxidation of iminium ions
  作者：Abdul Motaleb、Asish Bera、Pradip Maity

  DOI：10.1039/c8ob01032c

  日期：——

  A catalyst bound α-aminoalkyl radical intermediate from iminium is developed to control its formation and reactivity with aerobic oxygen. The influence of the catalyst was demonstrated via the ease of radical intermediate formation and its subsequent reactivity, including the first catalyst-controlled enantioselective aerobic oxidation with a chiral phosphite catalyst.

  研发了一种由催化剂与催化剂结合的亚胺基α-氨基烷基自由基中间体，以控制其形成和与好氧的反应性。通过容易形成自由基中间体及其随后的反应性证明了催化剂的影响，包括使用手性亚磷酸酯催化剂进行的第一催化剂控制的对映选择性好氧氧化反应。
• Phosphite‐Catalyzed C−H Allylation of Azaarenes via an Enantioselective [2,3]‐Aza‐Wittig Rearrangement
  作者：Abdul Motaleb、Soniya Rani、Tamal Das、Rajesh G. Gonnade、Pradip Maity

  DOI：10.1002/anie.201906681

  日期：2019.10

  A phosphite-mediated [2,3]-aza-Wittig rearrangement has been developed for the regio- and enantioselective allylic alkylation of six-membered heteroaromatic compounds (azaarenes). The nucleophilic phosphite adducts of N-allyl salts undergo a stereoselective base-mediated aza-Wittig rearrangement and dissociation of the chiral phosphite for overall C-H functionalization of azaarenes. This method provides

  已开发出亚磷酸酯介导的[2,3]-氮杂-维蒂希重排用于六元杂芳族化合物（氮杂芳烃）的区域和对映选择性烯丙基烷基化。N-烯丙基盐的亲核亚磷酸酯加合物经历了立体选择性碱基介导的氮杂-维蒂希重排和手性亚磷酸酯的解离，以实现氮杂芳烃的整体CH功能化。该方法可有效进入异喹啉，喹啉和吡啶体系中的叔手性和季手性中心，可同时承受烯丙基和氮杂芳烃上的多种取代基。还证明了用手性亚磷酸酯催化具有合成上有用的产率和对映选择性。
• PHOTOCHEMICAL METHODS OF MAKING CYCLOBUTANE BORONATES AND RELATED COMPOUNDS
  申请人：Wisconsin Alumni Research Foundation

  公开号：US20190040085A1

  公开（公告）日：2019-02-07

  The present technology relates generally cyclobutane boronates, including methods of preparation by exposing a mixture of a compound of Formula I in a solvent and a catalytic amount of a visible light sensitizer to provide a compound of Formula II, stereoisomers thereof, and/or salts of any of the foregoing. The cyclobutane boronate compounds are useful intermediates in the preparation of pharmaceutically active compounds as well as other other useful compounds.

  目前的技术通常涉及环丁烷硼酸酯，包括通过将化合物I的混合物暴露于溶剂和少量可见光敏化剂的方法来制备化合物II、其立体异构体和/或上述任何化合物的盐。环丁烷硼酸酯化合物是制备药用活性化合物以及其他有用化合物的中间体。
• Synthesis and Application of Chiral Phosphorus Ligands Derived from TADDOL for the Asymmetric Conjugate Addition of Diethyl Zinc to Enones
  作者：Alexandre Alexakis、Jonathan Burton、Johann Vastra、Cyril Benhaim、Xavier Fournioux、Alexandra van den Heuvel、Jean-Marc Levêque、Frédérique Mazé、Stephane Rosset

  DOI：10.1002/1099-0690(200012)2000:24<4011::aid-ejoc4011>3.0.co;2-d

  日期：2000.12

  been found to occur with 0.5% copper(II) triflate and 1% chiral phosphite. Cyclic phosphites derived from TADDOL gave excellent to moderate enantiomeric excesses. The nature of the exocyclic substituent of the dioxaphospholane ring is important, but the chiral induction is imposed by the TADDOL framework. Syntheses of all the TADDOL ligands are described.

  已发现二乙基锌与 2-环己烯、查耳酮和苯扎丙酮的不对称共轭加成与 0.5% 三氟甲磺酸铜 (II) 和 1% 手性亚磷酸酯一起发生。来自 TADDOL 的环状亚磷酸酯产生极好的至中等对映体过量。二氧杂膦环的环外取代基的性质很重要，但手性诱导是由 TADDOL 框架强加的。描述了所有 TADDOL 配体的合成。
• The preparation of optically active boronic ester substituted Δ2-isoxazolines
  作者：Richard H Wallace、K.K Zong

  DOI：10.1016/s0022-328x(99)00055-8

  日期：1999.6

  In this paper we report our recent results in the area of nitrile oxide cycloaddition to optically active vinylboronic esters to afford optically active boronic ester substituted Δ2-isoxazolines. In these studies, a number of optically active diols were investigated and TADDOLs have been found to afford the best diastereoselectivity. The mixture of diastereomers obtained in these reactions can be readily

  在本文中，我们报道我们最近在氧化腈环加成的光学活性vinylboronic酯的面积的结果，得到的光学活性的硼酸酯取代的Δ 2 -isoxazolines。在这些研究中，对许多旋光性二醇进行了研究，发现TADDOL具有最佳的非对映选择性。在这些反应中获得的非对映异构体混合物可以很容易地通过形成二乙醇胺-硼配合物进行纯化，并进行重结晶，从而获得纯的对映异构体。