(1R)-endo-(+)-3-diphenylphosphino-1,7,7-trimethylnorborn-2-one | 131339-30-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R)-endo-(+)-3-diphenylphosphino-1,7,7-trimethylnorborn-2-one
• 英文别名: (1R)-endo-(+)-3-(Diphenylphosphino)camphor；endo-3-diphenylphosphino-(1R)-(+)-camphor
• CAS: 131339-30-5
• 化学式: C₂₂H₂₅OP
• 分子量: 336.414
• InChiKey: TWMVZZSFPQEVRP-DXIQSLLYSA-N

物化性质

• 沸点：
  439.0±28.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.51
• 重原子数：
  24.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (1R)-endo-(+)-3-diphenylphosphino-1,7,7-trimethylnorborn-2-one 在 air 作用下， 以 乙醇 为溶剂， 以76%的产率得到(1R)-endo-(+)-3-(Diphenylphosphoryl)camphor
  参考文献：
  名称：

  Alkene epoxidation catalysed by camphor-derived β-ketophosphonate complexes of molybdenum(VI)

  摘要：

  New beta-ketophosphonates (L) have been prepared from (R)- or (S)-camphor with various substituents on the phosphorus atom [EtO, (R)- or (S)-Bu(s)O, Ph or binaphthoxy] and reacted with [MoO2Cl2] to form complexes [MoO(2)Cl(2)L]. These complexes have been used to give highly active catalysts for epoxidation of alkenes by Bu(t)OOH. Very fast initial rates (ca. 400 catalyst turnovers in the first minute) gave way to much slower rates because the hemi-labile beta-ketophosphonate is displaced by a diol ligand. In the presence of molecular sieves, the fast initial stage of the reaction is extended and for styrene, which gives low conversions followed by degradation in the absence of molecular sieves, styrene oxide can be formed with 98% conversion and 94% selectivity. It is demonstrated that both the Bu(t)OOH and the catalyst bind to the molecular sieves. the latter with loss of the beta-ketophosphonate ligand.

  DOI：

  10.1039/dt9950001221
• 作为产物：
  描述：

  (1R,3R,4S)-3-Diphenylphosphanyl-1,7,7-trimethyl-bicyclo[2.2.1]heptan-2-one 以 四氢呋喃 为溶剂， 生成 (1R)-endo-(+)-3-diphenylphosphino-1,7,7-trimethylnorborn-2-one
  参考文献：
  名称：

  Camphor-based β-hydroxyphosphoryl ligands and their complexes of the type [MoO(O₂)₂L(H₂O)]

  摘要：

  Homochiral hydroxyphosphoryl compounds, L, such as-the novel camphor-based(1R)-endo, endo-3S-(diphenylphosphoryl)-2R-hydroxybornane, have been found to be prevented from behaving as bidentate ligands in the epoxidation catalysts [MoO(O-2)(2)L(H2O)] by unexpectedly strong multiple-bond delocalisation producing near linear Mo-O-P angles.

  DOI：

  10.1039/dt9960004149

文献信息

• A new chiral metalladiphosphine for early–late chemistry. Crystal structure of a D-camphor-based zirconium enolato phosphine and rearrangement of heterobimetallic Zr/Pd complexes †
  作者：Chris Mattheis、Pierre Braunstein、Axel Fischer

  DOI：10.1039/b008227i

  日期：——

  (dmba = o-C6H4CH2NMe2) or [PdCl2(SEt2)2] led to complete transfer of the functional ligand to the Pd(II) centre, with formation of [(dmba)Pd(PPh2C10H14O)] 6 or cis-[Pd(PPh2C10H14O)2] 8 and [Cp2ZrCl2]/[Cp2TiCl2], respectively. A heterobimetallic Zr/Pd intermediate complex 10 of this rearrangement could be detected. Complexes 6 and 8 were prepared independently by reaction of 1 with [Pd(dmba)(μ-Cl)]2 or [Pd(SEt2)2Cl2]

  双（phosphinoenolato）锆2，从膦樟脑衍生物制备3-外型-PPh 2 Ç 10 ħ 15 Ô 1，表示第一Ç 2含有的早过渡金属中心-对称手性二膦系在膦基通过一个enolato连锁。它可以选择性地组装路易斯酸-酸早期-晚期双金属组合，例如Zr / Cu和Zr / Ag配合物4和5。还制备了单膦烯醇式钛茂3。2或3的反应与[Pd（dmba）（μ-Cl）] 2（dmba =  o -C 6 H 4 CH 2 NMe 2）或[PdCl 2（SEt 2）2 ]导致官能团的完全转移配体到Pd（II）中心，形成[[dmba）Pd（PPh 2 C 10 H 14 O ）] 6或顺式-[ Pd（PPh 2 C 10 H 14 O ）2 ] 8和[Cp 2 ZrCl 2 ] / [Cp 2 TiCl 2 ]。可以检测到这种重排的异双金属Zr / Pd中间配合物10。配合物6和8是通过1的反应独
• Camphor-derived β-ketophosphine complexes of palladium(<scp>II</scp>) and platinum(<scp>II</scp>)
  作者：D. Andrew Knight、David J. Cole-Hamilton、Domenico C. Cupertino

  DOI：10.1039/dt9900003051

  日期：——

  (L). This new chiral β-ketophosphine ligand reacts with [Pd(CH3CN)2Cl2] to give trans-[PdL2Cl2], and in a 1 : 1 ratio to give the chloro-bridged dimer [PdL(µ-Cl)Cl}2]. The ligand L reacts with [Pt(CH3CN)2Cl2] to give trans-[PtL2Cl2]. Thermolysis of [ML2Cl2](M = Pd or Pt) in refluxing xylene gives mixed phosphine–phosphinite complexes with mutually cis chlorides. The complex [PdL2Cl2] reacts with

  氯二苯基膦与烯醇锂的反应是用正丁基锂处理（1 R）-内-（+）-3-溴樟脑（樟脑=硼烷-2-一），得到（1 R）-内--（ +）-3-二苯基膦基樟脑（L）。这种新的手性β-酮膦配体与[Pd（CH 3 CN）2 Cl 2 ]反应生成反式-[PdL 2 Cl 2 ]，并以1：1的比例生成氯桥联的二聚体[PdL（µ -Cl）Cl} 2 ]。配体L与[Pt（CH 3 CN）2 Cl 2 ]反应，生成反式-[PtL 2Cl 2 ]。[ML 2 Cl 2 ]（M = Pd或Pt）在回流的二甲苯中热解，得到具有相互顺式氯化物的混合膦-次膦酸酯配合物。络合物[PdL 2 Cl 2 ]与过量的AgBF 4反应，得到[PdL 2 ] [BF 4 ] 2，显示其包含通过磷和酮氧原子的双齿结合。所有复合物的特征在于ir，1 H和31 P nmr光谱。
• The synthesis of endo-3-diphenylphosphino-(1R)-(+)-camphor (L) and some of its complexes with palladium(II), platinum(II) and rhodium(I); crystal structures of L and cis-[PdCl2L2]
  作者：Sarath D. Perera、Bernard L. Shaw、Mark Thornton-Pett、Jonathan D. Vessey

  DOI：10.1016/s0020-1693(00)92356-9

  日期：1992.8

  X-ray crystal structure of the cis -form 4b . Treatment of [PtCl 2 (COD)] with L, gives cis -[PtCl 2 L 2 ] ( 4c ) but with [PtCl 2 (NCMe) 2 ] the corresponding trans complex trans -[PtCl 2 L 2 ] ( 4d ) is formed. In compounds 4a-4d the PPh 2 groups are endo . The complexes of type [MCl 2 L 2 ] (MPd or Pt) are also formed by treating the bis-camphorphosphine enolates [M(PPh 2 C 10 H 14 O) 2 ] with

  用LiBu n处理Phase（1 R）-（+）-樟脑，然后用Ph 2 PCl处理，得到的主要产物是exo -3-diphenylphosphino-（1 R）-（+）-樟脑（3a）和一些相应的烯酸酯阴离子1。但是，在储存时，外膦3a异构化为相应的内膦3b，后者成为主要产物，并以70％的收率分离。确定了3b的晶体结构，并给出了详细的13 C和质子NMR数据。在氯仿溶液中，在乙酸作为催化剂的存在下，在两天内将内膦3b部分转化回外异构体3a。具有H 2 O 2的内膦3b（L）给出相应的氧化膦3c，与单斜晶硫形成相应的硫化膦3d。内-膦3b通过[PdCl 2（NCPh）2]得到[PdCl 2 L 2]，其以溶液形式存在顺式-反式混合物4a和4b。我们确定了顺式4b的X射线晶体结构。用L处理[PtCl 2（COD）]，得到顺式-[PtCl 2 L 2]（4c），但是用[PtCl 2（NCMe）2]处理，相应的反式复合物反式-[PtCl
• Camphor-derived β-ketophosphine complexes of rhodium(III) and iridium(III); x-ray crystal structure of cis,mer-trichlorobis[(1R)-endo-(+)-3-diphenylphosphinocamphor]rhodium(III) chloroform()
  作者：D.Andrew Knight、David J. Cole-Hamilton、Domenico C. Cupertino、Mary Harman、Michael B. Hursthouse

  DOI：10.1016/s0277-5387(00)83153-8

  日期：1992.1

  Reaction of (1 R)-endo-(+)-3-diphenylphosphinocamphor (L) with RhCl3-3H2O in ethanol gives trans,mer-[RhCl3L2] and in THF gives cis,mer-[RhCl3L2]. L reacts with IrCl3.3H2O to give trans,mer-[IrCl3L2]. On reaction with excess AgBF4, trans,mer-[IrCl3L2] gives cis,trans-[IrCl2L2]BF4. The complexes were characterized by IR, H-1 and P-31 NMR spectroscopy. Trans,mer-[MCl3L2] (M = Rh or Ir) and cis,mer-[RhCl3L2] show both unidentate and bidentate binding of L (through phosphorus and carbonyl oxygen atoms) and cis,trans-[IrCl2L2]BF4 shows only bidentate binding. The compound cis,mer-[RhCl3L2] has been characterized crystallographically. The complex is a distorted octahedron about rhodium with the three chloride ligands having meridional geometry, and the ligand phosphorus atoms being cis to one another. The Rh-P bond length for the bidentate ligand is 2.339(6) angstrom and for the unidentate ligand is 2.268(6) angstrom. The bite angle for the bidentate ligand is 81.8(4)-degrees.