(S,S)-5,11,17,23-tetra-tert-butyl-25,27-dibutoxy-26,28-bis(1,1'-binaphthyl-2,2'-dioxyphosphanyloxy)calix[4]arene | 1235590-80-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (S,S)-5,11,17,23-tetra-tert-butyl-25,27-dibutoxy-26,28-bis(1,1'-binaphthyl-2,2'-dioxyphosphanyloxy)calix[4]arene
• CAS: 1235590-80-3
• 化学式: C₉₂H₉₄O₈P₂
• 分子量: 1389.7
• InChiKey: AOUDNLWLVCRWNO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  27.41
• 重原子数：
  102.0
• 可旋转键数：
  12.0
• 环数：
  15.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  89.48
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 (S,S)-5,11,17,23-tetra-tert-butyl-25,27-dibutoxy-26,28-bis(1,1'-binaphthyl-2,2'-dioxyphosphanyloxy)calix[4]arene 以 CDCl₃ 为溶剂， 生成 [((S,S)-5,11,17,23-tetra-tert-butyl-25,27-dibutoxy-26,28-bis(1,1'-binaphthyl-2,2'-dioxyphosphanyloxy)calix[4]arene)Rh(COD)]BF4
  参考文献：
  名称：

  Evaluation of calix[4]arene-based chiral diphosphite ligands in Rh-catalyzed asymmetric hydrogenation of simple dehydroamino acid derivatives

  摘要：

  The calix[4]arene framework was readily modified to generate a number of chiral BINOL-based diphosphite ligands (3) capable of forming in situ Rh-complexes which catalyzed the asymmetric hydrogenation of model substrates methyl-(Z)-2-(acetamido)acrylate (1a) and methyl-(Z)-2-(acetamido)cinnamate (1b). The (S,S)-catalyst generated the (R)-product. Upper rim (R-1) and 1,3-O-alkylation (R-2) substitution on the calixarene strongly influenced catalyst activity and chiral induction. Optimum results were obtained when RI was -C(CH3)(3) and R-2 was -CH2CH2CH3 (3b). Under optimized conditions, 3b hydrogenated la and 1b in 98 and 96% ee, respectively. Overall, better catalyst performance was observed for "locked" cone-conformers of 3, with higher activity evident for the less sterically hindered 1a (TOF up to 1300h(-1) at P(H-2) = 5 atm). (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2010.03.034
• 作为产物：
  描述：

  (R)-(1,1′-联萘-2,2′-二氧)氯膦 、 5,11,17,23-tetra-tert-butyl-25,27-dibutoxycalyx[4]arene 在 sodium hydride 作用下， 以 甲苯 、 mineral oil 为溶剂， 反应 18.0h， 以52%的产率得到(S,S)-5,11,17,23-tetra-tert-butyl-25,27-dibutoxy-26,28-bis(1,1'-binaphthyl-2,2'-dioxyphosphanyloxy)calix[4]arene
  参考文献：
  名称：

  Evaluation of calix[4]arene-based chiral diphosphite ligands in Rh-catalyzed asymmetric hydrogenation of simple dehydroamino acid derivatives

  摘要：

  The calix[4]arene framework was readily modified to generate a number of chiral BINOL-based diphosphite ligands (3) capable of forming in situ Rh-complexes which catalyzed the asymmetric hydrogenation of model substrates methyl-(Z)-2-(acetamido)acrylate (1a) and methyl-(Z)-2-(acetamido)cinnamate (1b). The (S,S)-catalyst generated the (R)-product. Upper rim (R-1) and 1,3-O-alkylation (R-2) substitution on the calixarene strongly influenced catalyst activity and chiral induction. Optimum results were obtained when RI was -C(CH3)(3) and R-2 was -CH2CH2CH3 (3b). Under optimized conditions, 3b hydrogenated la and 1b in 98 and 96% ee, respectively. Overall, better catalyst performance was observed for "locked" cone-conformers of 3, with higher activity evident for the less sterically hindered 1a (TOF up to 1300h(-1) at P(H-2) = 5 atm). (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2010.03.034