(1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol

• 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: (1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol
• 英文别名: (1S,2S,5R)-1-(diphenylphosphanylmethyl)-5-methyl-2-propan-2-ylcyclohexan-1-ol
• 化学式: C₂₃H₃₁OP
• 分子量: 354.472
• InChiKey: MNFCHTVGPRMLRG-WTIAFYNJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (-)-薄荷酮 在 sodium hydride 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 29.0h， 生成 (1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol
  参考文献：
  名称：

  Synthesis and characterization of a new enantiopure hydroxylated phosphine, its rhodium(I) and (III) complexes and their performance in catalytic carbonylation

  摘要：

  The enantiomerically pure hydroxylated phosphine (1S,2S.5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol 3 was prepared in a two-step stereoselective process from the commercially available and low cost (-)-menthone. Reaction of this new ligand with the appropriate rhodium precursor gave the respective Rh(I) and Rh(III) complexes. For rhodium(I) the binuclear complex tran-P,P-bis-{mu-chlorocarbonyl[(1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol-P]-rhodium(I)} 6 was obtained by reaction with [Rh(mu-Cl)(CO)(2)](2). For Rh(III), two isomeric edge-sharing bioctahedral (ESBO) complexes. tirans-O,O-trans-P.P-bis{(OC-6-32)-[mu-chlorodichloro[(1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methylcyclohexanol-O,P]rhodium(III) 7a and trans-O,O-cis-P,P-bis{(OC-6-32)-mu-chlorodichloro[(1S,2S,5R)-1-diphenyphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol-O,P]rhodium(III): 7b, and the partially hydrolyzed product, trans-O,O-cis-P,P-(OC-32)- mu-chloro-mu-hydroxo-tetrachlorobis[(1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol-O,P]dirhodium(III)} 8 were characterized in solid state by single-crystal X ray diffraction analysis. The O-axial-P-equatorial trans-O,O arrangements observed in compounds 7a,b and 8 are preferred over the more common O-equatorial-P-equatorial Structure, presumably due to the stereo-electronic coordination preferences of the chiral hydroxylated phosphine. To the best Of Our knowledge, the ligand arrangement observed in 7b and 8 is unique among ESBO complexes. The rhodium(I) complex 6 is active as a catalyst precursor in the hydroformylation of styrene. yielding initial turnover frequencies up to 440 h(-1) and selectivities up to 74% in the branched aldehyde. Unfortunately, no enantiomeric excesses have been observed within experimental error. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00488-9
• 作为试剂：
  描述：

  苯乙烯 、 一氧化碳 在 di(rhodium)tetracarbonyl dichloride 氢气 、 (1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol 作用下， 以 甲苯 为溶剂， 80.0 ℃ 、2.0 MPa 条件下， 反应 24.0h， 生成 苯丙醛 、 2-苯基丙醛
  参考文献：
  名称：

  Synthesis and characterization of a new enantiopure hydroxylated phosphine, its rhodium(I) and (III) complexes and their performance in catalytic carbonylation

  摘要：

  The enantiomerically pure hydroxylated phosphine (1S,2S.5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol 3 was prepared in a two-step stereoselective process from the commercially available and low cost (-)-menthone. Reaction of this new ligand with the appropriate rhodium precursor gave the respective Rh(I) and Rh(III) complexes. For rhodium(I) the binuclear complex tran-P,P-bis-{mu-chlorocarbonyl[(1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol-P]-rhodium(I)} 6 was obtained by reaction with [Rh(mu-Cl)(CO)(2)](2). For Rh(III), two isomeric edge-sharing bioctahedral (ESBO) complexes. tirans-O,O-trans-P.P-bis{(OC-6-32)-[mu-chlorodichloro[(1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methylcyclohexanol-O,P]rhodium(III) 7a and trans-O,O-cis-P,P-bis{(OC-6-32)-mu-chlorodichloro[(1S,2S,5R)-1-diphenyphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol-O,P]rhodium(III): 7b, and the partially hydrolyzed product, trans-O,O-cis-P,P-(OC-32)- mu-chloro-mu-hydroxo-tetrachlorobis[(1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol-O,P]dirhodium(III)} 8 were characterized in solid state by single-crystal X ray diffraction analysis. The O-axial-P-equatorial trans-O,O arrangements observed in compounds 7a,b and 8 are preferred over the more common O-equatorial-P-equatorial Structure, presumably due to the stereo-electronic coordination preferences of the chiral hydroxylated phosphine. To the best Of Our knowledge, the ligand arrangement observed in 7b and 8 is unique among ESBO complexes. The rhodium(I) complex 6 is active as a catalyst precursor in the hydroformylation of styrene. yielding initial turnover frequencies up to 440 h(-1) and selectivities up to 74% in the branched aldehyde. Unfortunately, no enantiomeric excesses have been observed within experimental error. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00488-9

文献信息

• Synthesis and characterization of a new enantiopure hydroxylated phosphine, its rhodium(I) and (III) complexes and their performance in catalytic carbonylation
  作者：Josep Duran、Daniel Oliver、Alfonso Polo、Julio Real、Jordi Benet-Buchholz、Xavier Fontrodona

  DOI：10.1016/s0957-4166(03)00488-9

  日期：2003.9

  The enantiomerically pure hydroxylated phosphine (1S,2S.5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol 3 was prepared in a two-step stereoselective process from the commercially available and low cost (-)-menthone. Reaction of this new ligand with the appropriate rhodium precursor gave the respective Rh(I) and Rh(III) complexes. For rhodium(I) the binuclear complex tran-P,P-bis-mu-chlorocarbonyl[(1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol-P]-rhodium(I)} 6 was obtained by reaction with [Rh(mu-Cl)(CO)(2)](2). For Rh(III), two isomeric edge-sharing bioctahedral (ESBO) complexes. tirans-O,O-trans-P.P-bis(OC-6-32)-[mu-chlorodichloro[(1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methylcyclohexanol-O,P]rhodium(III) 7a and trans-O,O-cis-P,P-bis(OC-6-32)-mu-chlorodichloro[(1S,2S,5R)-1-diphenyphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol-O,P]rhodium(III): 7b, and the partially hydrolyzed product, trans-O,O-cis-P,P-(OC-32)- mu-chloro-mu-hydroxo-tetrachlorobis[(1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol-O,P]dirhodium(III)} 8 were characterized in solid state by single-crystal X ray diffraction analysis. The O-axial-P-equatorial trans-O,O arrangements observed in compounds 7a,b and 8 are preferred over the more common O-equatorial-P-equatorial Structure, presumably due to the stereo-electronic coordination preferences of the chiral hydroxylated phosphine. To the best Of Our knowledge, the ligand arrangement observed in 7b and 8 is unique among ESBO complexes. The rhodium(I) complex 6 is active as a catalyst precursor in the hydroformylation of styrene. yielding initial turnover frequencies up to 440 h(-1) and selectivities up to 74% in the branched aldehyde. Unfortunately, no enantiomeric excesses have been observed within experimental error. (C) 2003 Elsevier Ltd. All rights reserved.