2-(1-phenylethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane 2-oxide

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: 2-(1-phenylethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane 2-oxide
• 英文别名: 4,4,5,5-tetramethyl-2-(1-phenylethyl)-1,3,2-dioxaphospholane 2-oxide；4,4,5,5-Tetramethyl-2-(1-phenylethyl)-1,3,2lambda5-dioxaphospholane 2-oxide；4,4,5,5-tetramethyl-2-(1-phenylethyl)-1,3,2λ5-dioxaphospholane 2-oxide
• 化学式: C₁₄H₂₁O₃P
• 分子量: 268.293
• InChiKey: VWFDLZHETMGUHD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  苯乙烯 、 4,4,5,5-tetramethyl<1,3,2>dioxaphospholane-2-oxide 在 Me₂Pd(PPh₂Cy)₂ 作用下， 以 1,4-二氧六环 为溶剂， 反应 15.0h， 以100%的产率得到2-(1-phenylethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane 2-oxide
  参考文献：
  名称：

  五元环状膦酸氢盐的高反应性导致开发容易的钯催化烯烃的氢化磷酸化

  摘要：

  DOI：

  10.1021/ja000444v

文献信息

• A New Class of 3′-Sulfonyl BINAPHOS Ligands: Modulation of Activity and Selectivity in Asymmetric Palladium-Catalysed Hydrophosphorylation of Styrene
  作者：Katalin Barta、Giancarlo Franciò、Walter Leitner、Guy C. Lloyd-Jones、Ian R. Shepperson

  DOI：10.1002/adsc.200800366

  日期：2008.9.5

  (R)-8a–j with (S)-1,1′-binaphthalene-2,2′-dioxychlorophosphine (S)-9 generates 3′-sulfonyl BINAPHOS ligands (R,S)-10a–j in good yields (43–82%). These new ligands are of utlility in the asymmetric hydrophosphonylation of styrene (1) by 4,4,5,5-tetramethyl-1,3,2-dioxaphospholane 2-oxide (2), for which a combination of the chiral ligands with either [Pd(Cp)(allyl)] or [Pd(allyl)(MeCN)2]+/NaCH(CO2Me)2 proves

  BINOL（R F = CF 3或C 4 F 9）的BINOL （R）-2,2'-双全氟烷磺酸的钯催化的单芳基次膦酸酯[Ar 2 P（O）H]的单磷酸化反应，然后还原氧化膦（Cl 3然后用二异丙基氨基锂介导的阴离子硫杂-弗里斯重排提供对映体纯的（R）-2'-二芳基膦基2'-羟基3'-全氟烷磺酰基-1,1'-联萘[[ R）-8ab和（R）-8g –j ]，可通过格氏试剂（RMgX）介导的CF 3-置换[ （R）-8c–f ]。（耦合ř） - 8A-J与（小号）-1,1'-联二萘-2,2'-二dioxychlorophOSphine（小号） - 9生成3'-磺酰BINAPHOS配体（[R ，小号） - 10A-J中良好收率（43–82％）。这些新的配体在将苯乙烯（1）通过4,4,5,5-四甲基-1,3,2-二氧杂膦环氧化物2-氧化物（2）进行不对称氢膦酰化反应中具有实用性，为此手性配体与[Pd
• Regio- and Enantioselective Catalytic Hydrophosphorylation of Vinylarenes
  作者：Mstislav O. Shulyupin、Giancarlo Franciò、Irina P. Beletskaya、Walter Leitner

  DOI：10.1002/adsc.200404390

  日期：2005.4

  Regioselective and stereoselective hydrophosphorylation of vinylarenes 1 with pinacol H-phosphonate 2 can be achieved with transition metal catalysts. The use of rhodium catalysts such as the Wilkinson complex leads to the anti-Markovnikov adducts 3 as the only observable reaction products. In contrast, palladium catalysts give high selectivities for the Markovnikov adducts 4. In the presence of (R

  乙烯基芳烃1与频哪醇H-膦酸酯2的区域选择性和立体选择性加氢磷酸化可通过过渡金属催化剂实现。铑催化剂如威尔金森配合物的使用导致反马尔科夫尼科夫加合物3是唯一可观察到的反应产物。相比之下，钯催化剂对马尔可夫尼科夫加合物4具有较高的选择性。在（R，S）-BINAPHOS作为手性配体的存在下，首次在磷酸化反应中获得了显着的对映选择性。
• Processes for the preparation of phosphonic esters
  申请人：——

  公开号：US20030105345A1

  公开（公告）日：2003-06-05

  The present invention relates to a new manufacturing method for phosphonate esters, which have utility as a carbon-carbon binding formation agent, as well as a synthesis intermediate for biologically active substances such as medical drugs and agri-chemicals. Specifically the present invention relates to a new industrially advantageous manufacturing method for phosphonate esters in which the phosphonate esters of the subject can be efficiently obtained with a high yield rate through a simple operation while having barely any side reaction or sub-product. More specifically, the present invention pertains to a manufacturing method for phosphonate esters in which secondary phosphonate esters and alkene compounds are reacted in a transition metal medium. In addition the present invention relates to a new manufacturing method for allylphosphonate esters in which secondary cyclic phosphonate esters and 1,3-diene compounds are reacted in a palladium medium.

  本发明涉及一种新的膦酸酯制造方法，膦酸酯可用作碳碳结合形成剂，也可用作生物活性物质（如医疗药物和农用化学品）的合成中间体。 具体地说，本发明涉及一种新的具有工业优势的膦酸酯制造方法，在该方法中，可以通过简单的操作以高产率有效地获得主题的膦酸酯，同时几乎没有任何副反应或副产品。 更具体地说，本发明涉及一种膦酸酯的制造方法，其中仲膦酸酯和烯化合物在过渡金属介质中发生反应。此外，本发明还涉及一种烯丙基膦酸酯的新制造方法，其中仲环膦酸酯和 1，3-二烯化合物在钯介质中发生反应。
• Method for manufacturing phosphonate esters
  申请人：——

  公开号：US20040220422A1

  公开（公告）日：2004-11-04

  The present invention relates to a new manufacturing method for phosphonate esters, which have utility as a carbon-carbon binding formation agent, as well as a synthesis intermediate for biologically active substances such as medical drugs and agri-chemicals. Specifically the present invention relates to a new industrially advantageous manufacturing method for phosphonate esters in which the phosphonate esters of the subject can be efficiently obtained with a high yield rate through a simple operation while having barely any side reaction or sub-product. More specifically, the present invention pertains to a manufacturing method for phosphonate esters in which secondary phosphonate esters and alkene compounds are reacted in a transition metal catalyst. In addition the present invention relates to a new manufacturing method for allylphosphonate esters in which secondary cyclic phosphonate esters and 1,3-diene compounds are reacted in a palladium catalvst.

  本发明涉及一种新的膦酸酯制造方法，膦酸酯可用作碳碳结合形成剂，也可用作生物活性物质（如医疗药物和农用化学品）的合成中间体。 具体地说，本发明涉及一种新的具有工业优势的膦酸酯制造方法，在该方法中，可以通过简单的操作以高产率有效地获得主题的膦酸酯，同时几乎没有任何副反应或副产品。 更具体地说，本发明涉及一种膦酸酯的制造方法，其中仲膦酸酯和烯化合物在过渡金属催化剂中发生反应。此外，本发明还涉及一种新的烯丙基膦酸酯制造方法，其中仲环膦酸酯和 1,3 二烯化合物在钯催化剂中发生反应。
• Palladium-Catalyzed Hydrophosphonylation of Alkenes with Dialkyl H-Phosphonates
  作者：Mathieu Candy、Sophie A. L. Rousseaux、Alberto Cirugeda San Román、Monika Szymczyk、Pawel Kafarski、Eric Leclerc、Emmanuel Vrancken、Jean-Marc Campagne

  DOI：10.1002/adsc.201400190

  日期：2014.8.11

  AbstractThe palladium‐catalyzed hydrophosphonylation of alkenes with previously unreactive acyclic dialkyl H‐phosphonates has been developed. A catalyst system based on palladium/DavePhos or palladium/SPhos enables the transformation of various alkenes to phosphonates in moderate to good yields and with excellent levels of regioselectivity. Hydrophosphonylations with internal, disubstituted and/or unactivated alkenes are also reported.magnified image