(2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole) | 154598-63-7

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: (2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole)
• 英文别名: (2S,4S)-2,4-bis(dibenzophospholyl)pentane；5-[(2S,4S)-4-benzo[b]phosphindol-5-ylpentan-2-yl]benzo[b]phosphindole
• CAS: 154598-63-7
• 化学式: C₂₉H₂₆P₂
• 分子量: 436.473
• InChiKey: IWZCHTWGRDZHML-SFTDATJTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  31
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  bis(acetonitrile)dichloroplatinum(II) 、 (2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole) 以 甲苯 为溶剂， 生成 trans-[PtCl2((2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole))]2
  参考文献：
  名称：

  Synthesis of Pt compounds containing chiral (2S,4S) -pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole) as ligand and their use in asymmetric hydroformylation of styrene derivatives

  摘要：

  Unlike bis(diphenyl)phosphine derivatives in general, (2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole), S,S-BDBPP, gives a trans oligomeric compound [PtCl2(S,S-BDBPP)](n), 1, in reaction with dichloro-Pt precursors such as PtCl2(PhCN)(2), PtCl2(CH3CN)(2) and PtCl2(COD) at room temperature. Compound 1, which could be readily isolated, slowly rearranges in solutions at room temperature to the expected cis-monomer PtCl2(S,S-BDBPP), 3. Heating or the presence of PtCl2(COD) accelerates the transformation of compound 1 to 3. SnCl2 adducts of both compounds, trans-[PtCl(SnCl3)(S,S-BDBPP)](n), 2, and cis-PtCl(SnCl3)(S,S-BDBPP), 4, as well as the known cis-PtCl(SnCl3)(S,S-BDPP), 5, (S,S-BDPP = (2S,4S)-2,4-bis(diphenylphosphino)pentane have been tested as catalysts in the asymmetric hydroformylation of p-isobutylstyrene. The phenyl analog 5 provides up to 75% e.e. bur moderate yields to chiral 2-(4-isobutylphenyl)-2-propanal. Compared to this, the regioselectivity to the branched aldehyde is remarkably increased; however, the enantioselectivity is drastically decreased by the use of both dibenzophosphole derivatives 2 and 4. The similarities in the selectivities provided by 2 and 4 indicate that the trans oligomer 2 transforms to the cis-monomer 4 during the catalytic process, X-ray crystal structure determination of compound 3 shows a half-chair conformation for the chelate ring with a symmetric arrangement of dibenzophosphole groups. Besides a preference for the latter achiral conformation, the planar structure of the dibenzophosphole groups can also be considered as reason for the moderate enantioselectivities provided by 4. (C) 1997 Elsevier Science S.A.

  DOI：

  10.1016/s0022-328x(97)00130-7
• 作为产物：
  描述：

  5-苯基-5H-苯并[B]膦吲哚 、 (2R,4R)-2,4-pentanediol ditosylate 在 氯代叔丁烷 、 lithium 作用下， 生成 (2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole)
  参考文献：
  名称：

  Synthesis of Pt compounds containing chiral (2S,4S) -pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole) as ligand and their use in asymmetric hydroformylation of styrene derivatives

  摘要：

  Unlike bis(diphenyl)phosphine derivatives in general, (2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole), S,S-BDBPP, gives a trans oligomeric compound [PtCl2(S,S-BDBPP)](n), 1, in reaction with dichloro-Pt precursors such as PtCl2(PhCN)(2), PtCl2(CH3CN)(2) and PtCl2(COD) at room temperature. Compound 1, which could be readily isolated, slowly rearranges in solutions at room temperature to the expected cis-monomer PtCl2(S,S-BDBPP), 3. Heating or the presence of PtCl2(COD) accelerates the transformation of compound 1 to 3. SnCl2 adducts of both compounds, trans-[PtCl(SnCl3)(S,S-BDBPP)](n), 2, and cis-PtCl(SnCl3)(S,S-BDBPP), 4, as well as the known cis-PtCl(SnCl3)(S,S-BDPP), 5, (S,S-BDPP = (2S,4S)-2,4-bis(diphenylphosphino)pentane have been tested as catalysts in the asymmetric hydroformylation of p-isobutylstyrene. The phenyl analog 5 provides up to 75% e.e. bur moderate yields to chiral 2-(4-isobutylphenyl)-2-propanal. Compared to this, the regioselectivity to the branched aldehyde is remarkably increased; however, the enantioselectivity is drastically decreased by the use of both dibenzophosphole derivatives 2 and 4. The similarities in the selectivities provided by 2 and 4 indicate that the trans oligomer 2 transforms to the cis-monomer 4 during the catalytic process, X-ray crystal structure determination of compound 3 shows a half-chair conformation for the chelate ring with a symmetric arrangement of dibenzophosphole groups. Besides a preference for the latter achiral conformation, the planar structure of the dibenzophosphole groups can also be considered as reason for the moderate enantioselectivities provided by 4. (C) 1997 Elsevier Science S.A.

  DOI：

  10.1016/s0022-328x(97)00130-7

文献信息

• Synthesis of Pt compounds containing chiral (2S,4S) -pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole) as ligand and their use in asymmetric hydroformylation of styrene derivatives
  作者：Imre Tóth、Cornelis J. Elsevier、Johannes G. de Vries、József Bakos、Wilberth J.J. Smeets、Anthony L. Spek

  DOI：10.1016/s0022-328x(97)00130-7

  日期：1997.8

  Unlike bis(diphenyl)phosphine derivatives in general, (2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole), S,S-BDBPP, gives a trans oligomeric compound [PtCl2(S,S-BDBPP)](n), 1, in reaction with dichloro-Pt precursors such as PtCl2(PhCN)(2), PtCl2(CH3CN)(2) and PtCl2(COD) at room temperature. Compound 1, which could be readily isolated, slowly rearranges in solutions at room temperature to the expected cis-monomer PtCl2(S,S-BDBPP), 3. Heating or the presence of PtCl2(COD) accelerates the transformation of compound 1 to 3. SnCl2 adducts of both compounds, trans-[PtCl(SnCl3)(S,S-BDBPP)](n), 2, and cis-PtCl(SnCl3)(S,S-BDBPP), 4, as well as the known cis-PtCl(SnCl3)(S,S-BDPP), 5, (S,S-BDPP = (2S,4S)-2,4-bis(diphenylphosphino)pentane have been tested as catalysts in the asymmetric hydroformylation of p-isobutylstyrene. The phenyl analog 5 provides up to 75% e.e. bur moderate yields to chiral 2-(4-isobutylphenyl)-2-propanal. Compared to this, the regioselectivity to the branched aldehyde is remarkably increased; however, the enantioselectivity is drastically decreased by the use of both dibenzophosphole derivatives 2 and 4. The similarities in the selectivities provided by 2 and 4 indicate that the trans oligomer 2 transforms to the cis-monomer 4 during the catalytic process, X-ray crystal structure determination of compound 3 shows a half-chair conformation for the chelate ring with a symmetric arrangement of dibenzophosphole groups. Besides a preference for the latter achiral conformation, the planar structure of the dibenzophosphole groups can also be considered as reason for the moderate enantioselectivities provided by 4. (C) 1997 Elsevier Science S.A.