(4S)-2-[(1S)-7'-(二苯基膦基)-2,2',3,3'-四氢-1,1'-螺双[1H-茚]-7-基]-4,5-二氢-4-(苯基甲基)-恶唑 | 913829-88-6

• 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: (4S)-2-[(1S)-7'-(二苯基膦基)-2,2',3,3'-四氢-1,1'-螺双[1H-茚]-7-基]-4,5-二氢-4-(苯基甲基)-恶唑
• 中文别名: (4S)-2-[(1S)-7'-(二苯基膦)-2,2',3,3'-四氢-1,1'-螺二[1H-茚]-7-基]-4,5-二氢-4-苄基恶唑
• 英文名称: (S,S)-7-[4-(benzyl)oxazol-2-yl]-7'-diphenylphosphinyl-1,1'-spirobiindane
• 英文别名: (Sa,S)-Ph-Bn-SIPHOX；(4S)-4-Benzyl-2-[(1S)-7'-(diphenylphosphanyl)-2,2',3,3'-tetrahydro-1,1'-spirobi[inden]-7-yl]-4,5-dihydro-1,3-oxazole；[(3S)-4-[(4S)-4-benzyl-4,5-dihydro-1,3-oxazol-2-yl]-3,3'-spirobi[1,2-dihydroindene]-4'-yl]-diphenylphosphane
• CAS: 913829-88-6
• 化学式: C₃₉H₃₄NOP
• 分子量: 563.679
• InChiKey: WDIPXXMCRPGMIB-XSEQESSCSA-N

物化性质

• 熔点：
  164-166°C
• 比旋光度：
  -227.0° (c 0.5, CH2Cl2)
• 沸点：
  702.3±60.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9
• 重原子数：
  42
• 可旋转键数：
  6
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

SDS

---

Section 1: Product Identification
(S)-(-)-7-[4(S)-(Benzyl)oxazol-2-yl]-7-diphenylphosphino-2,2’,3,3’-tetrahydro-1,1'-spiroiindane, min. 97%
Chemical Name:
(Sa,S)-Ph-Bn-SIPHOX
CAS Registry Number: 913829-88-6
Formula: C39H34NOP
EINECS Number: none
Chemical Family: organophosphine ligand
Synonym: (Ra,S)-Ph-Bn-SIPHOX

---

Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 913829-88-6 100% no data no data

---

Section 3: Hazards Identification
Emergency Overview: Irritating to skin, eyes and respiratory tract.
Primary Routes of Exposure: Ingestion, inhalation, 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. May be harmful if swallowed.
Acute Health Affects: Irritating to skin, eyes and respiratory tract.
Chronic Health Affects: No information on long-term chronic effects.
NTP: No
IARC: No
OSHA: No

---

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: no data
Autoignition Temperature: no data
Explosion Limits: no data
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 irritating fumes.
Decomposion Products:
Unusual Fire or Explosion Hazards: No unusual fire or explosion hazards.

---

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

---

SECTION 7: Handling and Storage
Store in a tightly sealed container under an inert atmosphere of nitrogen or argon. Keep in a cool, dry,
Handling and Storage:
well-ventilated place.

---

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: 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.

---

SECTION 9: Physical and Chemical Properties
Color and Form: white solid
Molecular Weight: 563.67
Melting Point: 164-166°
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: none
Solubility in Water: insoluble

---

SECTION 10: Stability and Reactivity
Stability: moisture sensitive
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: prolonged exposure to moisture
Incompatibility: strong oxidizing agents
Decomposition Products: carbon monoxide, carbon dioxide, phosphorus oxides and organic fumes.

---

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): Not regulated under SARA 313
Second Ingredient: none

---

SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  sodium tetrakis[3,5-bis-(trifluoromethyl)phenyl]borate dihydrate 、 (4S)-2-[(1S)-7'-(二苯基膦基)-2,2',3,3'-四氢-1,1'-螺双[1H-茚]-7-基]-4,5-二氢-4-(苯基甲基)-恶唑 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 以 二氯甲烷 为溶剂， 以85%的产率得到(Sa,S)-[(C8H12)Ir(P(phenyl)2C8H7CC8H7C3NOH3(benzyl))][tetrakis[3,5-bis(trifluoromethyl)phenyl]borate]
  参考文献：
  名称：

  定义明确的手性螺铱/膦-恶唑啉阳离子配合物，用于在环境压力下对亚胺进行高度对映选择性氢化

  摘要：

  从光学纯的 7-diphenylphosphino-7'-trifluoromethanesulfonyloxyl-1,1'-spirobindane 开始，分四步合成了具有刚性和庞大螺二茚烷支架的新型手性膦-恶唑啉配体（7，SIPHOX），总含量为 40-64%屈服。铱配合物 7，Crabtree 催化剂的手性类似物，是通过配体 7 和 [Ir(COD)Cl](2) 在 tetrakis-3,5-bis(trifluoromethyl)phenylborate 钠存在下的配位生成的。通过NMR、ESI-MS和X-射线衍射分析表征配合物。Ir-SIPHOX 配合物可以在环境压力下催化无环 N-芳基酮亚胺的氢化，具有出色的对映选择性（高达 97% ee）和完全转化。该结果代表了最高的对映选择性和在环境压力下由 Crabtree 催化剂的手性类似物催化的亚胺氢化的第一个例子。对催化剂稳定性的研究表明，Ir-SIPHOX

  DOI：

  10.1021/ja063444p
• 作为产物：
  描述：

  (S)-7-diphenylphosphino-7'-carbomethoxy-1,1'-spirobiindane 在 4-甲氨基吡啶 、 氢氧化钾 、 1-羟基苯并三唑 、 甲基磺酰氯 、 三乙胺 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 生成 (4S)-2-[(1S)-7'-(二苯基膦基)-2,2',3,3'-四氢-1,1'-螺双[1H-茚]-7-基]-4,5-二氢-4-(苯基甲基)-恶唑
  参考文献：
  名称：

  定义明确的手性螺铱/膦-恶唑啉阳离子配合物，用于在环境压力下对亚胺进行高度对映选择性氢化

  摘要：

  从光学纯的 7-diphenylphosphino-7'-trifluoromethanesulfonyloxyl-1,1'-spirobindane 开始，分四步合成了具有刚性和庞大螺二茚烷支架的新型手性膦-恶唑啉配体（7，SIPHOX），总含量为 40-64%屈服。铱配合物 7，Crabtree 催化剂的手性类似物，是通过配体 7 和 [Ir(COD)Cl](2) 在 tetrakis-3,5-bis(trifluoromethyl)phenylborate 钠存在下的配位生成的。通过NMR、ESI-MS和X-射线衍射分析表征配合物。Ir-SIPHOX 配合物可以在环境压力下催化无环 N-芳基酮亚胺的氢化，具有出色的对映选择性（高达 97% ee）和完全转化。该结果代表了最高的对映选择性和在环境压力下由 Crabtree 催化剂的手性类似物催化的亚胺氢化的第一个例子。对催化剂稳定性的研究表明，Ir-SIPHOX

  DOI：

  10.1021/ja063444p
• 作为试剂：
  描述：

  2-phenyl-2-vinyloxetane 、 在 (4S)-2-[(1S)-7'-(二苯基膦基)-2,2',3,3'-四氢-1,1'-螺双[1H-茚]-7-基]-4,5-二氢-4-(苯基甲基)-恶唑 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 作用下， 以 二氯甲烷 为溶剂， 反应 19.0h， 以88%的产率得到(R,E)-8-(4-chlorophenyl)-4-phenyl-1-tosyl-1,5,6,8-tetrahydro-2H-benzofuro[2,3-c][1,5]oxazecine
  参考文献：
  名称：

  Pd催化的乙烯基氧杂环丁烷与氮杂二烯的对映选择性[6 + 4]环加成反应，从而获得十元杂环。

  摘要：

  我们在此报告了乙烯基氧杂环丁烷的第一个对映选择性环加成反应，其与氮杂二烯的反应通过[6 + 4]环加成反应提供了前所未有的十元杂环访问途径。通过使用市售的手性Pd-SIPHOX催化剂，可以以优异的收率和对映选择性获得各种苯并呋喃以及吲哚稠合的杂环。还发现了独特的路易斯酸诱导的这些十元杂环的断裂。

  DOI：

  10.1002/anie.201711648

文献信息

• Well-Defined Chiral Spiro Iridium/Phosphine−Oxazoline Cationic Complexes for Highly Enantioselective Hydrogenation of Imines at Ambient Pressure
  作者：Shou-Fei Zhu、Jian-Bo Xie、Yong-Zhen Zhang、Shen Li、Qi-Lin Zhou

  DOI：10.1021/ja063444p

  日期：2006.10.1

  catalyze the hydrogenation of acyclic N-aryl ketimines under ambient pressure with excellent enantioselectivities (up to 97% ee) and full conversions. This result represents the highest enantioselectivity and the first example of the hydrogenation of imines catalyzed by chiral analogues of the Crabtree catalyst at ambient pressure. Studies on the stability of the catalysts revealed that the catalysts Ir-SIPHOX

  从光学纯的 7-diphenylphosphino-7'-trifluoromethanesulfonyloxyl-1,1'-spirobindane 开始，分四步合成了具有刚性和庞大螺二茚烷支架的新型手性膦-恶唑啉配体（7，SIPHOX），总含量为 40-64%屈服。铱配合物 7，Crabtree 催化剂的手性类似物，是通过配体 7 和 [Ir(COD)Cl](2) 在 tetrakis-3,5-bis(trifluoromethyl)phenylborate 钠存在下的配位生成的。通过NMR、ESI-MS和X-射线衍射分析表征配合物。Ir-SIPHOX 配合物可以在环境压力下催化无环 N-芳基酮亚胺的氢化，具有出色的对映选择性（高达 97% ee）和完全转化。该结果代表了最高的对映选择性和在环境压力下由 Crabtree 催化剂的手性类似物催化的亚胺氢化的第一个例子。对催化剂稳定性的研究表明，Ir-SIPHOX