| 166330-13-8

• CAS: 166330-13-8；261926-75-4
• 化学式: C₅₈H₄₈O₂P₃Rh
• 分子量: 972.845
• InChiKey: UONGHWVQWOQEOB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  、 C13取代的一氧化碳 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  New Diphosphine Ligands Based on Heterocyclic Aromatics Inducing Very High Regioselectivity in Rhodium-Catalyzed Hydroformylation: Effect of the Bite Angle

  摘要：

  The effect of the bite angle on regioselectivity in the rhodium-catalyzed hydroformylation reaction was studied with a series of bidentate diphosphines based on xanthene-like backbones as ligands. The bite angles of these ligands are fine-tuned by subtle alterations of the backbone of the ligands. When the bridge (X) in the 10-position of xanthene is varied, the bite angle as calculated from molecular mechanics increases stepwise from 102 to 131 degrees, whereas the changes in steric bulk and electronic effects are virtually absent for the following ligands: bis(2-(diphenylphosphino)phenyl) ether (DPEphos, 1), X = H, H; 4,6-bis(diphenylphosphino)-10,10-dimethylphenoxasilin (Sixantphos, 2), X = Si(CH3)(2); 2,8-dimethyl-4,6-bis(diphenylphosphino)phenoxathiin (Thixantphos, 3), X = S; 9,9-dimethyl-4,6-bis(diphenylphosphino)xanthene (Xantphos, 4), X = C(CH3)(2); 4,6-bis(diphenylphosphino)dibenzofuran (DBFphos, 5), X = bond. In the hydroformylation of 1-octene the regioselectivity increased. regularly with increasing bite angle: at 40 degrees C up to 98.3% n-aldehyde was obtained with Xantphos, without isomerization or hydrogenation of 1-octene. DBFphos does not form chelates, and consequently no increased selectivity was observed. The selectivity of the catalyst was almost unaffected by raising of the temperature to 80 degrees C, resulting in a higher turnover frequency (tof) with a constant selectivity: 97.7% n-aldehyde, 0.5% isomerization, and a tof value of 800 mol (mel of Rh)(-1) h(-1). Xantphos induces the highest selectivity for the formation of the linear aldehyde reported for diphosphines in the hydroformylation of 1-alkenes until now. The complexes (diphosphine)Rh(H)(CO)(PPh(3)) and (diphosphine)Rh(H)(CO)(2) were prepared and identified with H-1, P-31, and C-13 NMR. The enhanced selectivity to the linear aldehyde was also observed for styrene (70% n-aldehyde with xantphos compared to 11% with triphenylphosphine). An X-ray crystal structure of the Xantphos ligand is presented (orthorhombic, space group Pbnm, with a = 8.7678(8) Angstrom, b = 18.967(1) Angstrom, c = 19.181(1) Angstrom, V = 3189.8(4) Angstrom(3), and Z = 4).

  DOI：

  10.1021/om00006a057
• 作为产物：
  描述：

  4,5-双二苯基膦-9,9-二甲基氧杂蒽 、 三(三苯基膦)羰基氢化铑 以 苯 为溶剂， 生成
  参考文献：
  名称：

  New Diphosphine Ligands Based on Heterocyclic Aromatics Inducing Very High Regioselectivity in Rhodium-Catalyzed Hydroformylation: Effect of the Bite Angle

  摘要：

  The effect of the bite angle on regioselectivity in the rhodium-catalyzed hydroformylation reaction was studied with a series of bidentate diphosphines based on xanthene-like backbones as ligands. The bite angles of these ligands are fine-tuned by subtle alterations of the backbone of the ligands. When the bridge (X) in the 10-position of xanthene is varied, the bite angle as calculated from molecular mechanics increases stepwise from 102 to 131 degrees, whereas the changes in steric bulk and electronic effects are virtually absent for the following ligands: bis(2-(diphenylphosphino)phenyl) ether (DPEphos, 1), X = H, H; 4,6-bis(diphenylphosphino)-10,10-dimethylphenoxasilin (Sixantphos, 2), X = Si(CH3)(2); 2,8-dimethyl-4,6-bis(diphenylphosphino)phenoxathiin (Thixantphos, 3), X = S; 9,9-dimethyl-4,6-bis(diphenylphosphino)xanthene (Xantphos, 4), X = C(CH3)(2); 4,6-bis(diphenylphosphino)dibenzofuran (DBFphos, 5), X = bond. In the hydroformylation of 1-octene the regioselectivity increased. regularly with increasing bite angle: at 40 degrees C up to 98.3% n-aldehyde was obtained with Xantphos, without isomerization or hydrogenation of 1-octene. DBFphos does not form chelates, and consequently no increased selectivity was observed. The selectivity of the catalyst was almost unaffected by raising of the temperature to 80 degrees C, resulting in a higher turnover frequency (tof) with a constant selectivity: 97.7% n-aldehyde, 0.5% isomerization, and a tof value of 800 mol (mel of Rh)(-1) h(-1). Xantphos induces the highest selectivity for the formation of the linear aldehyde reported for diphosphines in the hydroformylation of 1-alkenes until now. The complexes (diphosphine)Rh(H)(CO)(PPh(3)) and (diphosphine)Rh(H)(CO)(2) were prepared and identified with H-1, P-31, and C-13 NMR. The enhanced selectivity to the linear aldehyde was also observed for styrene (70% n-aldehyde with xantphos compared to 11% with triphenylphosphine). An X-ray crystal structure of the Xantphos ligand is presented (orthorhombic, space group Pbnm, with a = 8.7678(8) Angstrom, b = 18.967(1) Angstrom, c = 19.181(1) Angstrom, V = 3189.8(4) Angstrom(3), and Z = 4).

  DOI：

  10.1021/om00006a057

文献信息

• Rh-catalyzed C–C bond cleavage by transfer hydroformylation
  作者：Stephen K. Murphy、Jung-Woo Park、Faben A. Cruz、Vy M. Dong

  DOI：10.1126/science.1261232

  日期：2015.1.2

  that a rhodium catalyst can achieve selective dehydroformylation of a diverse range of compounds under mild conditions (see the Perspective by Landis). The protocol relies on effective transfer of the CO and H2 equivalents to a sacrificial strained olefin added to the mix. Science, this issue p. 56; see also p. 29 A catalyst to selectively reverse a common chemical reaction offers versatile opportunities

  加氢甲酰化转化为逆反应 加氢甲酰化反应在化学工业中被大规模应用，通过向烯烃中加入氢气和一氧化碳来制备醛。反向过程也可以证明在修饰复杂分子以进行药物研究方面很有用，但是针对此目的的方法通常会在没有氢气的情况下去除 CO。墨菲等人。现在表明，铑催化剂可以在温和条件下实现多种化合物的选择性脱氢甲酰化（参见 Landis 的观点）。该协议依赖于将 CO 和 H2 等价物有效转移到添加到混合物中的牺牲应变烯烃。科学，这个问题 p。56; 另见第。29 选择性逆转常见化学反应的催化剂为分子合成提供了多种机会。[另请参阅 Landis 的观点] 醛脱氢甲酰化生成烯烃的过程发生在各种甾醇（包括人体胆固醇）的生物合成过程中。在这里，我们实施了一个合成版本，其特征是甲酰基和氢化物从醛底物转移到应变的烯烃受体。铑（Xantphos）（苯甲酸酯）催化剂以高化学选择性活化醛碳-氢（C-H）键以触发碳-碳（C-C）键断裂并在低负载（0