(R)-1-[(Sp)-2-(dicyclohexylphosphino)ferrocenylethyl]diphenylphosphine | 158923-09-2

• 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
• 英文名称: (R)-1-[(Sp)-2-(dicyclohexylphosphino)ferrocenylethyl]diphenylphosphine
• 英文别名: (R,Sp)-Josiphos；SL-J004-1；(S)-1-[(Rp)-2-(Dicyclohexylphosphino)ferrocenyl]ethyldiphenylphosphine；cyclopenta-1,3-diene;dicyclohexyl-[2-[(1R)-1-diphenylphosphanylethyl]cyclopenta-1,3-dien-1-yl]phosphane;iron(2+)
• CAS: 158923-09-2
• 化学式: C₃₆H₄₄FeP₂
• 分子量: 594.54
• InChiKey: ABDQIEHFQHRVIN-KHZPMNTOSA-N

物化性质

• 比旋光度：
  -100° ±5° (c 0.5, CHCl3)

计算性质

• 辛醇/水分配系数(LogP)：
  9.77
• 重原子数：
  39
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 安全说明：
  S26,S36/37/39
• 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-Dicyclohexylphosphino)ferrocenyl]ethyldiphenylphosphine, min. 97%
CAS Registry Number: 158923-09-2
Formula: C36H44FeP2
EINECS Number: None
Chemical Family: organophosphine ligand
Synonym: [(S)-1-(R)-(-)-2(Diphenylphosphanylethyl)dicyclohexyl phosphanylferrocene

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title Compound 158923-09-2 100% no data no data

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Section 3: Hazards Identification
Emergency Overview: Irritating to skin, eyes and mucous membranes. 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: 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.
The toxicological properties of this compound have not been thoroughly investigated. Unrecognized hazards
Chronic Health Affects:
may be present.
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.

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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.

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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.

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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.

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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.
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.

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SECTION 9: Physical and Chemical Properties
Color and Form: orange powder
Molecular Weight: 594.59
Melting Point: no data
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: none
Solubility in Water: Insoluble

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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, and iron oxide.

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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 local, state and federal 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：

  bis(1,5-cyclooctadiene)nickel (0) 、 (R)-1-[(Sp)-2-(dicyclohexylphosphino)ferrocenylethyl]diphenylphosphine 反应 0.33h， 以88%的产率得到
  参考文献：
  名称：

  镍催化的丙酮与芳基氯化物和苯酚衍生物的单选择性α-芳基化反应。

  摘要：

  丙酮与芳基氯化物，新戊酸酯和氨基甲酸酯的具有挑战性的镍催化的单α-芳基化反应已首次实现。镍/ Josiphos基催化体系显示出独特的催化行为，可以高度选择性地形成所需的单α-芳基化丙酮。所开发的方法适用于各种（杂）芳基氯化物，包括生物学相关的衍生物。该方法已扩展到丙酮与苯酚衍生物的空前偶联。机理研究允许分离和表征关键的Ni 0和Ni II催化中间体。已证明Josiphos配体在稳定Ni II中间体以产生Ni 0方面起关键作用/ Ni II催化途径。然后利用对空气稳定的Ni II预催化剂，利用机理上的理解来改进方案。

  DOI：

  10.1002/anie.202006826
• 作为产物：
  描述：

  二环己基氯化膦 、 diphenyl(1-ferrocenylethyl)phosphine 在 正丁基锂 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 1.5h， 以14%的产率得到(R)-1-[(Sp)-2-(dicyclohexylphosphino)ferrocenylethyl]diphenylphosphine
  参考文献：
  名称：

  Synthesis of ferrocene-based phosphine ligands via Cu-catalyzed reductive coupling of ferrocenyl ketone-derived tosylhydrazones and H -phosphorus oxides

  摘要：

  Ferrocene-based phosphine oxides with various substituents at phosphorous atoms were synthesized by Cu-catalyzed reductive coupling of ferrocenyl ketone-derived tosylhydrazones and H-phosphorus oxides. Followed by the reduction of ferrocene-based phosphine oxides, 1-substituted ferrocene-based phosphine ligand 7 and 1,1'-disubstituted ferrocene-based phosphine ligand 9 were obtained. Josiphos type ligand 8 were produced after ortho-lithiation of 7 and trapping with chlorodiphenyl phosphine or chlorodicyclohexylphosphine. (C) 2016 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2016.11.054
• 作为试剂：
  描述：

  ISOBUTYLMAGNESIUM BROMIDE 、 (E)-2-styrylbenzoxazole 在 copper(I) bromide dimethylsulfide complex 、 (R)-1-[(Sp)-2-(dicyclohexylphosphino)ferrocenylethyl]diphenylphosphine 、 三氟化硼乙醚 作用下， 以 乙醚 为溶剂， 反应 18.0h， 以65%的产率得到
  参考文献：
  名称：

  格氏试剂催化不对称加成到烯基取代的芳族 N-杂环

  摘要：

  铜不对称地添加烷基 含氮环是现代药物分子结构中非常常见的特征。因此，可以选择性修饰这些 N 杂环的反应对于优化药物特性特别有用。朱姆德等人。开发了一种方法，以单个镜像方向将烷基附加到从 N 杂环悬空的取代的 C=C 双键上。依赖格氏试剂引入烷基的铜催化反应在广泛的底物范围内表现出高选择性，不受氮的干扰。科学，这个问题 p。433 手性铜催化剂将一类在药物化学研究中感兴趣的化合物烷基化。催化不对称共轭加成反应代表了在当代有机合成中获取手性分子的强大策略。然而，它们对共轭链烯基-N-杂芳族化合物的适用性，在药物化学中特别感兴趣，落后于其他底物的应用。我们报告了一种高度对映选择性和化学选择性催化转化的范围广泛的 β-取代的共轭烯基-N-杂芳烃到其相应的手性烷基化产物。这种操作简单的方法可以在 β 碳位置引入直链、支链和环状烷基链以及苯基。这一成功的关键是通过路易斯酸活化增强烯基-杂芳族底物的反应性，

  DOI：

  10.1126/science.aaf1983

文献信息

• Asymmetric Transfer Hydrogenation of Ketones Catalyzed by Rhenium Complexes with Chiral Ferrocenylphosphane Ligands
  作者：Esteban Mejía、Raphael Aardoom、Antonio Togni

  DOI：10.1002/ejic.201200693

  日期：2012.11

  rhenium complexes containing chiral ferrocenyldiphosphane ligands of the Josiphos family, starting from commercially available rhenium sources. These new ReV oxido and nitrido complexes, several of which have been characterized by X-ray crystallography, are air- and moisture-stable and are active catalysts in the asymmetric transfer hydrogenation of ketones using 2-propanol as the hydrogen source in

  我们从市售的铼来源开始，制备了一系列含有 Josiphos 家族手性二茂铁基二膦配体的新型铼配合物。这些新的 ReV 氧化和氮化配合物，其中一些已通过 X 射线晶体学表征，对空气和湿气稳定，并且是在使用 2-丙醇作为氢源的酮不对称转移氢化中的活性催化剂。亚化学计量的三乙胺 (TEA)。反应以良好到极好的收率（50-99%）顺利进行，但对映选择性适中（高达 58% ee）。提出了一种不涉及氢化物的机制。
• Nickel-Catalyzed Amination of Aryl Chlorides with Ammonia or Ammonium Salts
  作者：Rebecca A. Green、John F. Hartwig

  DOI：10.1002/anie.201500404

  日期：2015.3.16

  The nickel‐catalyzed amination of aryl chlorides to form primary arylamines occurs with ammonia or ammonium sulfate and a well‐defined single‐component nickel(0) precatalyst containing a Josiphos ligand and an η2‐bound benzonitrile ligand. This system also catalyzes the coupling of aryl chlorides with gaseous amines in the form of their hydrochloride salts.

  镍催化芳基氯化物胺化形成伯芳胺是用氨或硫酸铵和含有 Josiphos 配体和η 2结合苯甲腈配体的明确单组分镍 (0) 预催化剂发生的。该系统还催化芳基氯与盐酸盐形式的气态胺的偶联。
• Josiphos类手性二茂铁膦配体的合成方法
  申请人：河南省科学院化学研究所有限公司

  公开号：CN105949248B

  公开（公告）日：2018-08-07

  本发明公开了一种Josiphos 类手性二茂铁膦配体的合成方法，属于有机合成领域。该方法通过如下步骤实现：以二茂铁为起始原料，三氯化铝的催化剂，与膦氯化合物R2PCl反应，然后在三氯化铁和D‑脯氨酸的催化作用下与乙烯基二芳基膦反应得到Josiphos 类手性二茂铁膦配体。本发明与现有技术相比步骤少，操作简单，降低了生产成本，适合工业化生产。制得的Josiphos 类手性二茂铁膦配体可作为金属催化剂的配体，催化不对称有机反应，应用于医药合成等领域。
• On the Mechanism of the Copper-Catalyzed Enantioselective 1,4-Addition of Grignard Reagents to α,β-Unsaturated Carbonyl Compounds
  作者：Syuzanna R. Harutyunyan、Fernando López、Wesley R. Browne、Arkaitz Correa、Diego Peña、Ramon Badorrey、Auke Meetsma、Adriaan J. Minnaard、Ben L. Feringa

  DOI：10.1021/ja0585634

  日期：2006.7.19

  The mechanism of the enantioselective 1,4-addition of Grignard reagents to alpha,beta-unsaturated carbonyl compounds promoted by copper complexes of chiral ferrocenyl diphosphines is explored through kinetic, spectroscopic, and electrochemical analysis. On the basis of these studies, a structure of the active catalyst is proposed. The roles of the solvent, copper halide, and the Grignard reagent have

  通过动力学、光谱和电化学分析探索了由手性二茂二膦的铜配合物促进的格氏试剂对映选择性 1,4-加成到 α、β-不饱和羰基化合物的机制。在这些研究的基础上，提出了活性催化剂的结构。已经检查了溶剂、卤化铜和格氏试剂的作用。动力学研究支持将还原消除作为涉及手性催化剂、底物和格氏试剂的限速步骤。热力学活化参数由反应速率的温度依赖性确定。讨论了假定的活性物质和反应的催化循环。
• Synthesis of new derivatives of copper complexes of Josiphos family ligands for applications in asymmetric catalysis
  作者：R. Oost、J. Rong、A. J. Minnaard、S. R. Harutyunyan

  DOI：10.1039/c4cy00180j

  日期：——

  A series of new copper complexes containing chiral ferrocenyl diphosphine ligands of the Josiphos family have been prepared. These complexes have been studied in the catalytic asymmetric 1,2-addition of Grignard reagents to enones and aromatic ketones. Variation of the electronic and steric properties of the ligand resulted in a positive effect in the regio- and enantioselectivity of Grignard reagents

  已经制备了一系列含有Josiphos家族的手性二茂铁基二膦配体的新的铜配合物。这些配合物已经在格氏试剂到烯酮和芳族酮的催化不对称1,2-加成中进行了研究。配体的电子和空间特性的变化对格氏试剂对α- H-取代的烯酮的区域和对映体选择性产生积极影响，其中叔酸在二芳基膦部分中引入了丁基取代基。铜配合物也成功地用于格氏试剂对烯酸酯的催化不对称共轭加成中。与线性配体rev-Josiphos相比，线性格氏试剂的催化不对称加成没有观察到对映选择性的提高。