(R)-(-)-1-{(S)-2-[双(3,5-二-三氟甲基苯基)膦]二茂铁基}乙基二-3,5-二甲苯基膦 | 166172-63-0

• 物质功能分类: 化学试剂 - 有机试剂 - 膦配体
• 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: (R)-(-)-1-{(S)-2-[双(3,5-二-三氟甲基苯基)膦]二茂铁基}乙基二-3,5-二甲苯基膦
• 中文别名: (R)-1-{(SP)-2-[双[3,5-双(三氟甲基)苯基]膦基]二茂铁基}乙基二(3,5-二甲苯基)膦；(1R)-1-[双[3,5-双(三氟甲基)苯基]膦基]-2-[(1R)-1-[双(3,5-二甲苯基)膦基]乙基]二茂铁(符合标准)；(R)-1-{(S)-2-[双[3,5-双(三氟甲基)苯基]膦基]二茂铁基}乙基二(3,5-二甲苯基)膦
• 英文名称: Josiphos SL-J008-1
• 英文别名: Iron(2+) 2-{bis[3,5-bis(trifluoromethyl)phenyl]phosphanyl}-1-{(1R)-1-[bis(3,5-dimethylphenyl)phosphanyl]ethyl}cyclopenta-2,4-dien-1-ide cyclopenta-2,4-dien-1-ide (1/1/1)；[(1R)-1-[2-bis[3,5-bis(trifluoromethyl)phenyl]phosphanylcyclopenta-1,4-dien-1-yl]ethyl]-bis(3,5-dimethylphenyl)phosphane;cyclopenta-1,3-diene;iron(2+)
• CAS: 166172-63-0
• 化学式: C₄₄H₃₆F₁₂FeP₂
• 分子量: 910.545
• InChiKey: OJJUNRXMQFVYEO-KHZPMNTOSA-N

物化性质

• 比旋光度：
  -280° ±10° (c 0.5, CHCl3)

计算性质

• 辛醇/水分配系数(LogP)：
  13.07
• 重原子数：
  59
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  14

安全信息

• 安全说明：
  S26
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 海关编码：
  29319090
• 危险性防范说明：
  P261,P280,P301+P312,P302+P352,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335

SDS

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Section 1: Product Identification
Chemical Name: (R)-(-)-1-{(S)-2-[Bis(3,5-di-trifluoromethylphenyl)phosphino]ferrocenyl}ethyldi-3,5-xylylphosphine, min. 97%
CAS Registry Number: 166172-63-0
Formula: C44H36F12FeP2
EINECS Number: None
Chemical Family: organophosphine ligand
Synonym: None

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title Compound 166172-63-0 100% 2.5mg/m3 (as F) 2.5mg/m3 (as F)

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Section 3: Hazards Identification
Emergency Overview: Irritating to skin, and eyes. May be irritating to the respiratory tract. May be harmful if swallowed.
Primary Routes of Exposure: Ingestion, eyes
Eye Contact: Causes slight to mild irritation of the eyes.
Skin Contact: Causes slight to mild irritation of the skin.
Inhalation: May be 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 and eyes. May be irritating to the respiratory tract.
Product contains fluorine which, under certain conditions of use, decomposition or metabolism, may generate
Chronic Health Affects: fluoride ion causing nausea, vomiting, labored breathing, hypocalcaemia, deterioration of bone and tooth
structure and kidney and liver damage.
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 with water. Remove contaminated clothes if necessary. Seek medical assistance if
Skin Exposure:
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.

---

SECTION 5: Fire Fighting Measures
Flash Point: not applicable
Autoignition Temperature: none
Explosion Limits: none
Extinguishing Medium: carbon dioxide, foam or dry powder
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 and vapors of phosphorus pentoxide.
Decomposion Products:
Unusual Fire or Explosion Hazards: No unusual fire or explosion hazards.

---

SECTION 6: Accidental Release Measures
Small spills can be mixed with vermiculite, sodium carbonate or other suitable non combustible adsorbent and
Spill and Leak Procedures:
swept up.

---

SECTION 7: Handling and Storage
Keep material in a tightly sealed container. Prolonged exposure to the air will result in degradation of the
Handling and Storage:
product. Handle and store material under an inert atmosphere of nitrogen or argon.

---

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.
Ventilation: Material may form a fine dust. If possible, 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: Material may form a fine dust. If possible, handle the material in an efficient fume hood.
Additional Protection: No additional protection required.

---

SECTION 9: Physical and Chemical Properties
Color and Form: orange pwdr.
Molecular Weight: 910.57
Melting Point: no data
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: none
Solubility in Water: Insoluble

---

SECTION 10: Stability and Reactivity
Stability: air and moisture stable
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: exposure to oxygen, contact with strong oxidizing agents
Incompatibility: Oxidizing agents and halogens
Decomposition Products: carbon dioxide, carbon monoxide, organic fumes, phosphorus oxides, fluoroorganics, and iron oxide.

---

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

---

SECTION 12: Ecological Information
Ecological Information: No information available

---

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

---

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

---

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

---

SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  (R)-(-)-1-{(S)-2-[双(3,5-二-三氟甲基苯基)膦]二茂铁基}乙基二-3,5-二甲苯基膦 、 cobalt(II) bromide 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  炔烃和烯基衍生物催化对映选择性合成环丁烯

  摘要：

  使用可扩展且环境友好的化学方法，发现用于从容易获得的前体制备手​​性化合物的对映选择性催化反应，可以极大地影响它们的设计、合成和最终的规模制造。功能化环丁烷和环丁烯是许多生物活性天然产物和药学相关小分子中的重要结构基序。它们也是其他类别有机化合物的有用前体，例如其他环烷烃衍生物、杂环化合物、立体定义的 1,3-二烯和催化不对称合成的配体。制造环丁烯的最简单方法是通过炔烃和烯基衍生物之间的对映选择性 [2+2]-环加成反应，这种反应历史悠久。然而，给出可接受的对映选择性的此类已知反应的范围非常窄，并且严格限于活化的炔烃和高反应性烯烃。在这里，我们公开了一种广泛适用的对映选择性 [2+2]-环加成反应，在各种炔烃和烯基衍生物（两种最丰富的有机前体类别）之间进行。关键的环加成反应使用衍生自易于合成的配体和地球上丰富的金属钴的催化剂。记录了 50 多种对映选择性在 86-97% ee 范围内的不同

  DOI：

  10.1021/jacs.9b07885
• 作为产物：
  描述：

  (S)-(-)-N,N-二甲基-1-二茂铁基乙胺 、 双(3,5-二甲苯基)磷 、 氯二[3,5-二(三氟甲基)苯基]膦 以 溶剂黄146 为溶剂， 生成 (R)-(-)-1-{(S)-2-[双(3,5-二-三氟甲基苯基)膦]二茂铁基}乙基二-3,5-二甲苯基膦
  参考文献：
  名称：

  可调谐的二茂铁基二膦配体用于N芳基亚胺的Ir催化对映选择性氢化

  摘要：

  二茂铁基二膦R 2 PF-P（R'）2是在碘化物和酸促进剂存在下铱催化的N-芳基亚胺对映体选择性氢化的有效，可调节的配体。发现了N-（2-乙基-6-甲基苯基）-N-（1'-甲氧基甲基）-亚乙基-胺（MEA-亚胺）和2,3,3-三甲基吲哚的氢化的结构-活性/选择性相关性（TMI）。使用[Ir（cod）Cl] 2和（R）-（S）-PPF-P（3,5-Xyl）2原位生成的催化剂观察到，MEA亚胺具有极高的催化活性和中等至良好的对映选择性。（xyliphos）。使用相同类型的催化剂，尽管具有较低的催化剂活性，但其他几种N-芳基亚胺也可以以31％至96％的对映选择性进行氢化。

  DOI：

  10.1016/s0022-328x(00)00766-x
• 作为试剂：
  描述：

  乙酰苯 在 吡啶 、 (R)-(-)-1-{(S)-2-[双(3,5-二-三氟甲基苯基)膦]二茂铁基}乙基二-3,5-二甲苯基膦 、 N,N-二异丙基乙胺 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 34.0h， 生成 rac-(3aR,8bR)-4-methylene-3,3a,4,8b-tetrahydro-2H-indeno[1,2-b]furan 、 (3aS,8bS)-4-methylene-3,3a,4,8b-tetrahydro-2H-indeno[1,2-b]furan
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Intermolecular Cyclization

  摘要：

  DOI：

  10.1002/anie.201303753

文献信息

• Enantioselective Synthesis of Cyclobutenes by Intermolecular [2+2] Cycloaddition with Non-<i>C</i>₂ Symmetric Digold Catalysts
  作者：Cristina García-Morales、Beatrice Ranieri、Imma Escofet、Laura López-Suarez、Carla Obradors、Andrey I. Konovalov、Antonio M. Echavarren

  DOI：10.1021/jacs.7b07651

  日期：2017.10.4

  The enantioselective intermolecular gold(I)-catalyzed [2+2] cycloaddition of terminal alkynes and alkenes has been achieved using non-C2-chiral Josiphos digold(I) complexes as catalysts, by the formation of the monocationic complex. This new approach has been applied to the enantioselective total synthesis of rumphellaone A.

  使用非 C2-手性 Josiphos digold(I) 配合物作为催化剂，通过形成单阳离子配合物，实现了对映选择性分子间金 (I) 催化的 [2+2] 环加成反应。这种新方法已应用于对映选择性全合成 rumphellaone A。
• Electrochemistry and complexation of Josiphos ligands
  作者：Brenna L. Ghent、Sarah L. Martinak、Lauren A. Sites、James A. Golen、Arnold L. Rheingold、Chip Nataro

  DOI：10.1016/j.jorganchem.2007.02.039

  日期：2007.5

  The oxidative electrochemistry of 11 chiral bis-phosphinoferrocene ligands, all within the Josiphos class of ligands, was examined in methylene chloride. The oxidation of these ligands displays multiple waves of varying chemical reversibility. Palladium(II) and platinum(II) complexes with the general formula [MCl2(P–P)] (M = Pd or Pt; P–P = Josiphos) were prepared, characterized by NMR and cyclic voltammetry

  在二氯甲烷中检查了全部属于Josiphos类配体的11个手性双膦二茂铁配体的氧化电化学。这些配体的氧化显示出多种具有不同化学可逆性的波。制备了具有通式[MCl 2（P–P）]（M = Pd或Pt； P–P = Josiphos）的钯（II）和铂（II）配合物，并通过NMR和循环伏安法进行了表征。当Josiphos配体配位时，电化学极大地简化了。报道了同一Josiphos配体的钯（II）和铂（II）配合物的X射线结构。
• Catalytic Enantioselective Synthesis of Cyclobutenes from Alkynes and Alkenyl Derivatives
  作者：Mahesh M. Parsutkar、Vinayak Vishnu Pagar、T. V. RajanBabu

  DOI：10.1021/jacs.9b07885

  日期：2019.9.25

  compounds from readily available precursors, using scalable and environmentally benign chemistry, can greatly impact their design, synthesis and eventually manufacture on scale. Functionalized cyclobutanes and cyclobutenes are important structural motifs seen in many bioactive natural products and pharmaceutically relevant small molecules. They are also useful precursors for other classes of organic compounds

  使用可扩展且环境友好的化学方法，发现用于从容易获得的前体制备手​​性化合物的对映选择性催化反应，可以极大地影响它们的设计、合成和最终的规模制造。功能化环丁烷和环丁烯是许多生物活性天然产物和药学相关小分子中的重要结构基序。它们也是其他类别有机化合物的有用前体，例如其他环烷烃衍生物、杂环化合物、立体定义的 1,3-二烯和催化不对称合成的配体。制造环丁烯的最简单方法是通过炔烃和烯基衍生物之间的对映选择性 [2+2]-环加成反应，这种反应历史悠久。然而，给出可接受的对映选择性的此类已知反应的范围非常窄，并且严格限于活化的炔烃和高反应性烯烃。在这里，我们公开了一种广泛适用的对映选择性 [2+2]-环加成反应，在各种炔烃和烯基衍生物（两种最丰富的有机前体类别）之间进行。关键的环加成反应使用衍生自易于合成的配体和地球上丰富的金属钴的催化剂。记录了 50 多种对映选择性在 86-97% ee 范围内的不同
• Tunable ferrocenyl diphosphine ligands for the Ir-catalyzed enantioselective hydrogenation of N-aryl imines
  作者：Hans-Ulrich Blaser*、Hans-Peter Buser、Robert Häusel、Hans-Peter Jalett、Felix Spindler*

  DOI：10.1016/s0022-328x(00)00766-x

  日期：2001.3

  Ferrocenyl diphosphines R2PF-P(R′)2 are effective, tunable ligands for the iridium catalyzed enantioselective hydrogenation of N-aryl imines in the presence of iodide and acid promoters. Structure–activity/selectivity correlations were found for the hydrogenation of N-(2-ethyl-6-methylphenyl)-N-(1′-methoxymethyl)-ethylidene-amine (MEA-imine) and for 2,3,3-trimethylindolenine (TMI). Extremely high catalytic

  二茂铁基二膦R 2 PF-P（R'）2是在碘化物和酸促进剂存在下铱催化的N-芳基亚胺对映体选择性氢化的有效，可调节的配体。发现了N-（2-乙基-6-甲基苯基）-N-（1'-甲氧基甲基）-亚乙基-胺（MEA-亚胺）和2,3,3-三甲基吲哚的氢化的结构-活性/选择性相关性（TMI）。使用[Ir（cod）Cl] 2和（R）-（S）-PPF-P（3,5-Xyl）2原位生成的催化剂观察到，MEA亚胺具有极高的催化活性和中等至良好的对映选择性。（xyliphos）。使用相同类型的催化剂，尽管具有较低的催化剂活性，但其他几种N-芳基亚胺也可以以31％至96％的对映选择性进行氢化。