(S)-4-phenyl-4,5-dihydro-3H-dinaphtho[2,1-c;1',2'-e]phosphepine oxide | 914253-11-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (S)-4-phenyl-4,5-dihydro-3H-dinaphtho[2,1-c;1',2'-e]phosphepine oxide
• 英文别名: 4-phenyl-3,5-dihydrodinaphtho[2,1-c:1',2'-e]phosphepine 4-oxide；13-Phenyl-13lambda5-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene 13-oxide；13-phenyl-13λ5-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene 13-oxide
• CAS: 914253-11-5
• 化学式: C₂₈H₂₁OP
• 分子量: 404.448
• InChiKey: BHTAJCCNIPGWCY-UHFFFAOYSA-N

物化性质

• 沸点：
  707.8±53.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  30
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-4-phenyl-4,5-dihydro-3H-dinaphtho[2,1-c;1',2'-e]phosphepine oxide 在 草酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 4-chloro-4-phenyl-4,5-dihydro-3H-dinaphtho[2,1-c:1',2'-e]phosphepin-4-ium chloride
  参考文献：
  名称：

  轻度一锅还原膦（III）及其金属催化剂上的膦（V）氧化物

  摘要：

  在温和的反应条件下，已经实现了使用草酰氯作为活化剂和六氯乙硅烷作为还原剂的一系列膦（V）氧化物的无金属还原。该方法成功地用于减少工业废物副产物三苯基膦（V）的氧化，关闭磷循环以干净地再生三苯基膦（III）。机理研究和量子化学计算支持中间体phospho盐的离解氯离子对乙硅烷硅的攻击，这是脱保护的限速步骤。

  DOI：

  10.1021/acs.organomet.0c00788
• 作为产物：
  描述：

  4-phenyl-4,5-dihydro-3H-dinaphtho<2,1-c;1',2'-e>phosphepine 在 双氧水 作用下， 以 水 、 丙酮 为溶剂， 反应 1.0h， 以75%的产率得到(S)-4-phenyl-4,5-dihydro-3H-dinaphtho[2,1-c;1',2'-e]phosphepine oxide
  参考文献：
  名称：

  Enantioselective rhodium-catalyzed hydrogenation of enol carbamates in the presence of monodentate phosphines

  摘要：

  The rhodium-catalyzed asymmetric hydrogenation of different acyclic and cyclic enol carbarnates to give optically active carbarnates has been examined in the presence of chiral monodentate ligands based on a 4,5-dihydro-3H-dinaphthophosphepine motif 4. The enantioselectivity is largely dependent upon the reaction conditions, the nature of substituents on the phosphorus ligand and structure of the enol carbamate. By applying the optimized reaction conditions, enantioselectivities of up to 96% ee have been achieved. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2007.06.001

文献信息

• A Mild One-Pot Reduction of Phosphine(V) Oxides Affording Phosphines(III) and Their Metal Catalysts
  作者：Łukasz Kapuśniak、Philipp N. Plessow、Damian Trzybiński、Krzysztof Woźniak、Peter Hofmann、Phillip Iain Jolly

  DOI：10.1021/acs.organomet.0c00788

  日期：2021.3.22

  metal-free reduction of a range of phosphine(V) oxides employing oxalyl chloride as an activating agent and hexachlorodisilane as reducing reagent has been achieved under mild reaction conditions. The method was successfully applied to the reduction of industrial waste byproduct triphenylphosphine(V) oxide, closing the phosphorus cycle to cleanly regenerate triphenylphosphine(III). Mechanistic studies and quantum

  在温和的反应条件下，已经实现了使用草酰氯作为活化剂和六氯乙硅烷作为还原剂的一系列膦（V）氧化物的无金属还原。该方法成功地用于减少工业废物副产物三苯基膦（V）的氧化，关闭磷循环以干净地再生三苯基膦（III）。机理研究和量子化学计算支持中间体phospho盐的离解氯离子对乙硅烷硅的攻击，这是脱保护的限速步骤。
• Enantioselective rhodium-catalyzed hydrogenation of enol carbamates in the presence of monodentate phosphines
  作者：Stephan Enthaler、Giulia Erre、Kathrin Junge、Dirk Michalik、Anke Spannenberg、Fabrizio Marras、Serafino Gladiali、Matthias Beller

  DOI：10.1016/j.tetasy.2007.06.001

  日期：2007.6

  The rhodium-catalyzed asymmetric hydrogenation of different acyclic and cyclic enol carbarnates to give optically active carbarnates has been examined in the presence of chiral monodentate ligands based on a 4,5-dihydro-3H-dinaphthophosphepine motif 4. The enantioselectivity is largely dependent upon the reaction conditions, the nature of substituents on the phosphorus ligand and structure of the enol carbamate. By applying the optimized reaction conditions, enantioselectivities of up to 96% ee have been achieved. (c) 2007 Elsevier Ltd. All rights reserved.