(2R)-2-[二苯基[(三甲基硅酯)氧基]甲基]-吡咯烷 | 943757-71-9

• 物质功能分类: 有机原料 - 有机硅化合物
• 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: (2R)-2-[二苯基[(三甲基硅酯)氧基]甲基]-吡咯烷
• 中文别名: (2R)-2-[二苯基[(三甲基硅基)氧基]甲基]吡咯烷；(R)-(+)-α,α-二苯基-2-吡咯烷甲醇三甲基硅基醚；R-二苯基脯氨醇三甲基硅醚
• 英文名称: (R)-2-(diphenyl(trimethylsilyloxy)methyl)pyrrolidine
• 英文别名: (R)-(-)-α,α-diphenyl-2-pyrrolidinemethanol trimethylsilyl ether；(2R)-2-(diphenyl((trimethylsilyl)oxy)methyl)pyrrolidine；(R)-diphenylprolinol trimethylsilyl ether；diphenylprolinol trimethylsilyl ether；(R)-2-diphenyltrimethylsiloxymethylpyrrolidine；Hayashi-Jorgensen catalyst；(R)-Hayashi catalyst；(R)-DPPOTMS；(R)-2-(Diphenyl((trimethylsilyl)oxy)methyl)pyrrolidine；[diphenyl-[(2R)-pyrrolidin-2-yl]methoxy]-trimethylsilane
• CAS: 943757-71-9
• 化学式: C₂₀H₂₇NOSi
• 分子量: 325.526
• InChiKey: RSUHWMSTWSSNOW-LJQANCHMSA-N

物化性质

• 沸点：
  412.7±35.0 °C(Predicted)
• 密度：
  1.021
• 闪点：
  >110℃

计算性质

• 辛醇/水分配系数(LogP)：
  4.53
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  21.3
• 氢给体数：
  1
• 氢受体数：
  2

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S26
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 海关编码：
  2933990090

SDS

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Section 1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product identifiers
: (R)-(+)-α,α-Diphenyl-2-pyrrolidinemethanol
Product name
trimethylsilyl ether
CAS-No. : 943757-71-9
Relevant identified uses of the substance or mixture and uses advised against
Identified uses : Laboratory chemicals, Manufacture of substances

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Section 2. HAZARDS IDENTIFICATION
Classification of the substance or mixture
Classification according to Regulation (EC) No 1272/2008 [EU-GHS/CLP]
Skin irritation (Category 2)
Eye irritation (Category 2)
Specific target organ toxicity - single exposure (Category 3)
Classification according to EU Directives 67/548/EEC or 1999/45/EC
Irritating to eyes, respiratory system and skin.
Label elements
Labelling according Regulation (EC) No 1272/2008 [CLP]
Pictogram
Signal word Warning
Hazard statement(s)
H315 Causes skin irritation.
H319 Causes serious eye irritation.
H335 May cause respiratory irritation.
Precautionary statement(s)
P261 Avoid breathing dust.
P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove
contact lenses, if present and easy to do. Continue rinsing.
Supplemental Hazard none
Statements
According to European Directive 67/548/EEC as amended.
Hazard symbol(s)
R-phrase(s)
R36/37/38 Irritating to eyes, respiratory system and skin.
S-phrase(s)
S26 In case of contact with eyes, rinse immediately with plenty of water and
seek medical advice.
Other hazards - none

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Section 3. COMPOSITION/INFORMATION ON INGREDIENTS
Substances
: (R)-α,α-Diphenylprolinol trimethylsilyl ether
Synonyms
(R)-2-[Diphenyl(trimethylsilanyloxy)methyl]pyrrolidine
(2R)-2-[Diphenyl[(trimethylsilyl)oxy]methyl]pyrrolidine
Formula : C20H27NOSi
Molecular Weight : 325,52 g/mol
Component Concentration
(R)-(+)-alpha ,alpha -Diphenyl-2-pyrrolidinemethanol trimethylsilyl ether
CAS-No. 943757-71-9 -

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Section 4. FIRST AID MEASURES
Description of first aid measures
General advice
Consult a physician. Show this safety data sheet to the doctor in attendance.
If inhaled
If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician.
In case of skin contact
Wash off with soap and plenty of water. Consult a physician.
In case of eye contact
Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.
If swallowed
Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician.
Most important symptoms and effects, both acute and delayed
To the best of our knowledge, the chemical, physical, and toxicological properties have not been
thoroughly investigated.
Indication of any immediate medical attention and special treatment needed
no data available

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Section 5. FIREFIGHTING MEASURES
Extinguishing media
Suitable extinguishing media
Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.
Special hazards arising from the substance or mixture
Carbon oxides, nitrogen oxides (NOx), silicon oxides
Advice for firefighters
Wear self contained breathing apparatus for fire fighting if necessary.
Further information
no data available

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Section 6. ACCIDENTAL RELEASE MEASURES
Personal precautions, protective equipment and emergency procedures
Use personal protective equipment. Avoid dust formation. Avoid breathing vapors, mist or gas. Ensure
adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust.
Environmental precautions
Do not let product enter drains.
Methods and materials for containment and cleaning up
Pick up and arrange disposal without creating dust. Sweep up and shovel. Keep in suitable, closed
containers for disposal.
Reference to other sections
For disposal see section 13.

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Section 7. HANDLING AND STORAGE
Precautions for safe handling
Avoid contact with skin and eyes. Avoid formation of dust and aerosols.
Provide appropriate exhaust ventilation at places where dust is formed.
Conditions for safe storage, including any incompatibilities
Store in cool place. Keep container tightly closed in a dry and well-ventilated place.
Recommended storage temperature: 2 - 8 °C
Specific end uses
no data available

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Section 8. EXPOSURE CONTROLS/PERSONAL PROTECTION
Control parameters
Components with workplace control parameters
Exposure controls
Appropriate engineering controls
Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and
at the end of workday.
Personal protective equipment
Eye/face protection
Safety glasses with side-shields conforming to EN166 Use equipment for eye protection tested
and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).
Skin protection
Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique
(without touching glove's outer surface) to avoid skin contact with this product. Dispose of
contaminated gloves after use in accordance with applicable laws and good laboratory practices.
Wash and dry hands.
The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and
the standard EN 374 derived from it.
Body Protection
impervious clothing, The type of protective equipment must be selected according to the
concentration and amount of the dangerous substance at the specific workplace.
Respiratory protection
For nuisance exposures use type P95 (US) or type P1 (EU EN 143) particle respirator.For higher
level protection use type OV/AG/P99 (US) or type ABEK-P2 (EU EN 143) respirator cartridges.
Use respirators and components tested and approved under appropriate government standards
such as NIOSH (US) or CEN (EU).

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Section 9. PHYSICAL AND CHEMICAL PROPERTIES
Information on basic physical and chemical properties
a) Appearance Form: solid
b) Odour no data available
c) Odour Threshold no data available
d) pH no data available
e) Melting point/freezing no data available
point
f) Initial boiling point and no data available
boiling range
g) Flash point > 110 °C - closed cup
h) Evaporation rate no data available
i) Flammability (solid, gas) no data available
j) Upper/lower no data available
flammability or
explosive limits
k) Vapour pressure no data available
l) Vapour density no data available
m) Relative density 1,0459 g/mL at 25 °C
n) Water solubility no data available
o) Partition coefficient: n- no data available
octanol/water
p) Autoignition no data available
temperature
q) Decomposition no data available
temperature
r) Viscosity no data available
s) Explosive properties no data available
t) Oxidizing properties no data available
Other safety information
no data available

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Section 10. STABILITY AND REACTIVITY
Reactivity
no data available
Chemical stability
no data available
Possibility of hazardous reactions
no data available
Conditions to avoid
no data available
Incompatible materials
Strong oxidizing agents
Hazardous decomposition products
Other decomposition products - no data available

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Section 11. TOXICOLOGICAL INFORMATION
Information on toxicological effects
Acute toxicity
no data available
Skin corrosion/irritation
no data available
Serious eye damage/eye irritation
no data available
Respiratory or skin sensitization
no data available
Germ cell mutagenicity
no data available
Carcinogenicity
IARC: No component of this product present at levels greater than or equal to 0.1% is identified as
probable, possible or confirmed human carcinogen by IARC.
Reproductive toxicity
no data available
Specific target organ toxicity - single exposure
Inhalation - May cause respiratory irritation.
Specific target organ toxicity - repeated exposure
no data available
Aspiration hazard
no data available
Potential health effects
Inhalation May be harmful if inhaled. Causes respiratory tract irritation.
Ingestion May be harmful if swallowed.
Skin May be harmful if absorbed through skin. Causes skin irritation.
Eyes Causes serious eye irritation.
Signs and Symptoms of Exposure
To the best of our knowledge, the chemical, physical, and toxicological properties have not been
thoroughly investigated.
Additional Information
RTECS: Not available

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Section 12. ECOLOGICAL INFORMATION
Toxicity
no data available
Persistence and degradability
no data available
Bioaccumulative potential
no data available
Mobility in soil
no data available
Results of PBT and vPvB assessment
no data available
Other adverse effects
no data available

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Section 13. DISPOSAL CONSIDERATIONS
Waste treatment methods
Product
Offer surplus and non-recyclable solutions to a licensed disposal company. Dissolve or mix the material
with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber.
Contaminated packaging
Dispose of as unused product.

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Section 14. TRANSPORT INFORMATION
UN number
ADR/RID: - IMDG: - IATA: -
UN proper shipping name
ADR/RID: Not dangerous goods
IMDG: Not dangerous goods
IATA: Not dangerous goods
Transport hazard class(es)
ADR/RID: - IMDG: - IATA: -
Packaging group
ADR/RID: - IMDG: - IATA: -
Environmental hazards
ADR/RID: no IMDG Marine pollutant: no IATA: no
Special precautions for user
no data available

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SECTION 15 - REGULATORY INFORMATION
N/A

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  (2R)-2-[二苯基[(三甲基硅酯)氧基]甲基]-吡咯烷 在 palladium on activated charcoal 、 氢气 、 N-甲基吗啉氧化物 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 苯甲酸 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 20.0~40.0 ℃ 、400.01 kPa 条件下， 反应 14.67h， 生成 tert-butyl (2S,3R)-2-formyl-3-(4-methoxyphenyl)-pyrrolidine-1-carboxylate
  参考文献：
  名称：

  EP2876105

  摘要：

  公开号：
• 作为产物：
  描述：

  三甲基氯硅烷 、 (R)-(+)-alpha,alpha-二苯基脯氨醇 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以97%的产率得到(2R)-2-[二苯基[(三甲基硅酯)氧基]甲基]-吡咯烷
  参考文献：
  名称：

  作为合成泊沙康唑的中间体化合物的制备方法及其制备的中间化合物

  摘要：

  本发明涉及一种作为合成药物泊沙康唑的中间体化合物的制备方法及其制备的中间化合物。本发明所提供的式I的化合物的制备方法包括以4‑(2，4‑二氟苯基)‑4‑烯戊酸甲酯或其还原产物4‑(2，4‑二氟苯基)‑4‑烯戊甲醛作为起始原料，在手性催化剂的存在下，在先与甲醛或多聚甲醛反应后，再经特性氧化、酯化反应和卤化成环反应，最后经水解和酸处理。本发明的制备方法具有反应条件温和、反应过程简单、目标产物总收率高且纯度高等优点，适合工业化生产。

  公开号：

  CN114591272A
• 作为试剂：
  描述：

  邻溴苯甲醛 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 正丁基锂 、 (2R)-2-[二苯基[(三甲基硅酯)氧基]甲基]-吡咯烷 、 triscarbonyl-(η⁴-3,4-bis(4-methoxyphenyl)-2,5-diphenylcyclopenta-2,4-dienone)iron 、 十二/十四烷基二甲基氧化胺 、 水 、 potassium carbonate 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 二氯甲烷 为溶剂， 反应 64.75h， 生成
  参考文献：
  名称：

  铁和有机催化借氢立体选择性构建四氢吡喃

  摘要：

  立体控制的 oxa-Michael 加成具有挑战性，因为该过程具有高度可逆性，最终导致新形成的立体中心外消旋化。当铁催化的烯丙醇借氢与立体控制的有机催化氧杂迈克尔加成相结合时，可以有效地制备多种手性四氢吡喃。该反应可以以非对映选择性方式从预先存在的立体中心进行或以对映选择性方式从非手性底物进行。成功的关键是铁络合物的反应活性，它对烯丙醇脱氢具有选择性，并不可逆地导致反应生成最终产物。

  DOI：

  10.1021/acs.orglett.4c01969

文献信息

• Unlocking Access to Enantiopure Fused Uracils by Chemodivergent [4+2] Cross‐Cycloadditions: DFT‐Supported Homo‐Synergistic Organocatalytic Approach
  作者：Claudio Curti、Gloria Rassu、Marco Lombardo、Vincenzo Zambrano、Luigi Pinna、Lucia Battistini、Andrea Sartori、Giorgio Pelosi、Franca Zanardi

  DOI：10.1002/anie.202007509

  日期：2020.11.2

  which embody a three‐dimensional and functional‐group‐rich architecture is a useful tool in medicinal chemistry oriented synthesis. In this work, an unprecedented amine‐catalyzed [4+2] cross‐cycloaddition is documented; it involves remotely enolizable 6‐methyluracil‐5‐carbaldehydes and β‐aryl enals, and chemoselectively produces two novel bicyclic and tricyclic fused uracil chemotypes in good yields

  化学方法的发现使构建融合了三维和功能基团的碳环尿嘧啶成为可能，这是面向药物化学合成的有用工具。在这项工作中，记录了前所未有的胺催化的[4 + 2]交叉环加成；它涉及可远程烯醇化的6-甲基尿嘧啶-5-甲醛和β-芳基烯醛，并且化学选择性产生两种新型双环和三环稠合尿嘧啶化学型，具有最高的对映体控制水平。深入的机理研究和对照实验支持了一种有趣的均相协同有机催化方法，其中相同的胺有机催化剂在逐步消除[4 + 2]的环加成中同时与两种醛伙伴结合，
• Enantioselective Organocatalytic Cascade Approach to Different Classes of Benzofused Acetals
  作者：Bruno Matos Paz、Lydia Klier、Line Naesborg、Vibeke Henriette Lauridsen、Frank Jensen、Karl Anker Jørgensen

  DOI：10.1002/chem.201602992

  日期：2016.11.14

  A novel enantioselective organocatalytic strategy is presented for the synthesis of tetrahydrofurobenzofuran and methanobenzodioxepine natural product core structures. The strategy is based on a pair of divergent reaction pathways in which hydroxyarenes react with γ‐keto‐α,β‐unsaturated aldehydes, catalyzed by a chiral secondary amine. One reaction pathway, which leads to chiral 5,5‐fused acetals with

  提出了一种新颖的对映选择性有机催化策略，用于合成四氢呋喃苯并呋喃和甲氧苯并二氧杂戊环酮天然产物核心结构。该策略基于一对不同的反应途径，在该途径中，羟基芳烃与手性仲胺催化的γ-酮-α，β-不饱和醛发生反应。一种反应途径可产生具有两个立体中心（四氢呋喃苯并呋喃支架）的手性5,5缩合乙缩醛，产率中等，收率可达96％  ee。另一个反应途径提供了具有三个立体中心的5,6桥联的甲基苯并二氧杂庚酸骨架，产率中等至良好，且ee高达95％ 。该反应是显着的，因为它可以以低至0.25 mol％的催化剂负载量进行，从而提供了亚胺离子催化中已知的最高周转率之一。此外，半缩醛四氢呋喃苯并呋喃可以进行官能化，包括还原，氧化和烯丙基化。最后，基于实验和计算研究，研究了不同途径的底物控制中涉及的作用。讨论了涉及空间，电子和立体电子相互作用的模型，以合理化观察到的选择性。
• Asymmetric synthesis of drug-like spiro[chroman-3,3′-indolin]-2′-ones through aminal-catalysis
  作者：Dhevalapally B. Ramachary、M. Shiva Prasad、S. Vijaya Laxmi、R. Madhavachary

  DOI：10.1039/c3ob42100g

  日期：——

  Asymmetric synthesis of drug-like functionalized spiro[chroman-3,3′-indolin]-2′-ones 5 containing three contiguous stereocenters with high diastereo- and enantioselectivities was achieved using the reflexive-Michael (r-M) reaction of unmodified hydroxyenals 1 with various (E)-3-alkylideneindolin-2-ones 2 in the presence of (R)-DPPOTMS/AcOH (R)-3/4b as a catalyst at room temperature. Chiral spiro[chroman-3,3′-indolin]-2′-ones 5 were transformed into the functionalized spiranes 7, 9, and 10 in good yields with high selectivity through Wittig, TCRA, acetal protection and reduction reactions, respectively. Supporting evidence for the reaction pathway through the formation of the important catalytic species of “aminals” was observed through NMR and ESI-HRMS analysis of an ongoing reaction between 1 and (R)-3 in CDCl3 and also shown by the structural requirement in hydroxyenals 1 to generate the “aminals” with (R)-3 through controlled experiments.

  成功实现了药物类似物功能化的Spiro[chroman-3,3′-indolin]-2′-酮5的非对称合成，该化合物含有三个相邻的立体中心，并具有高的二面体和对映选择性。通过在室温下，使用未修饰的羟基醛1与各种(E)-3-烯基吲哚-2-酮2的反射迈克尔（r-M）反应，在催化剂(R)-DPPOTMS/醋酸(R)-3/4b的存在下进行的合成。手性Spiro[chroman-3,3′-indolin]-2′-酮5经过维蒂希反应、TCRA反应、保护反应和还原反应相继转化为功能化的旋转体7、9和10，且均具有良好的产率和高选择性。通过NMR和ESI-HRMS分析观察到在CDCl3中1与(R)-3的进行反应中形成重要催化物种“亚胺”的反应途径的支持证据，并且通过对羟基醛1进行控制实验显示了生成“亚胺”与(R)-3之间的结构需求。
• Neighboring<i>ortho</i>-Hydroxy Group Directed Catalytic Asymmetric Triple Domino Reactions of Acetaldehyde with (<i>E</i>)-2-(2-Nitrovinyl)phenols
  作者：Dhevalapally B. Ramachary、P. Srinivasa Reddy、M. Shiva Prasad

  DOI：10.1002/ejoc.201402182

  日期：2014.5

  neighboring ortho-hydroxy group participation in the pretransition state of enamine- and iminium-based triple domino reactions for high reactions rates and asymmetric induction. Enantiomerically pure, drug-like chromanes and tetrahydro-6H-benzo[c]chromenes having three to four contiguous stereocenters are synthesized through triple domino Michael/aldol/oxa-Michael reactions catalyzed by (R)-2-diphenyl[(trim

  在此，我们展示了利用相邻的邻羟基参与基于烯胺和亚胺的三重多米诺反应的预转变状态，以实现高反应速率和不对称诱导。通过 (R)-2-二苯基 [(三甲基甲硅烷基) 催化的三重多米诺迈克尔/醛醇/氧杂-迈克尔反应合成对映体纯的药物样色满和四氢-6H-苯并[c]色烯具有三到四个连续的立体中心氧]甲基}吡咯烷，然后在温和条件下由简单前体进行 Wittig 和 Michael/Wittig-Horner 反应。
• Chiral Nitroarenes as Enantioselective Single-Electron-Transfer Oxidants for Carbene-Catalyzed Radical Reactions
  作者：Hongling Wang、Yuhuang Wang、Xingkuan Chen、Chengli Mou、Shuyan Yu、Huifang Chai、Zhichao Jin、Yonggui Robin Chi

  DOI：10.1021/acs.orglett.9b02736

  日期：2019.9.20

  A new class of chiral oxidants is developed. These readily accessible oxidants contain a nitro group for oxidation and a chiral sulfonamide moiety for stereoselectivity control. The chiral information from the oxidants can effectively transfer to the substrates in carbene-catalyzed β-hydroxylation of enals via single-electron-transfer radical processes. We expect these oxidants to find unique applications

  新型的手性氧化剂被开发出来。这些容易获得的氧化剂包含用于氧化的硝基和用于立体选择性控制的手性磺酰胺部分。来自氧化剂的手性信息可通过单电子转移自由基过程在卡宾催化的烯类的β-羟基化反应中有效转移至底物。我们希望这些氧化剂能在其他不对称氧化和氧原子转移反应中找到独特的应用。

表征谱图