(4R,5R)-4-diphenylphosphinomethyl-5-bis(4-N,N-dimethylaminophenyl)phosphinomethyl-2,2-dimethyl-1,3-dioxolane | 123135-89-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (4R,5R)-4-diphenylphosphinomethyl-5-bis(4-N,N-dimethylaminophenyl)phosphinomethyl-2,2-dimethyl-1,3-dioxolane
• 英文别名: (4R,5R)-4-diphenylphosphinomethyl-5-bis(4-N,N-dimethylaminophenyl)phosphinomethyl-2,2-dimethyl-1,3-dioxolan；4-[[4-(dimethylamino)phenyl]-[[(4R,5R)-5-(diphenylphosphanylmethyl)-2,2-dimethyl-1,3-dioxolan-4-yl]methyl]phosphanyl]-N,N-dimethylaniline
• CAS: 123135-89-7
• 化学式: C₃₅H₄₂N₂O₂P₂
• 分子量: 584.678
• InChiKey: XOOZIUWTMVXGIK-HEVIKAOCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  41.0
• 可旋转键数：
  10.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  24.94
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium 、 (4R,5R)-4-diphenylphosphinomethyl-5-bis(4-N,N-dimethylaminophenyl)phosphinomethyl-2,2-dimethyl-1,3-dioxolane 、 silver tetrafluoroborate 以 甲醇 、 二氯甲烷 为溶剂， 以88.2%的产率得到{{(4R,5R)-4-diphenylphosphinomethyl-5-bis(4-N,N-dimethylaminomethylphenyl)phosphinomethyl-2,2-dimethyl-1,3-dioxolane}(η4-1,5-cyclooctadiene)}rhodium(I) tetrafluoroborate
  参考文献：
  名称：

  对称性不对称的羰基氨基丙烯酸酯和（Z）-乙酰氨基-季铵甲酯和铑-（Diop-Derivat）-Komplexen als Katalysatoren。EinflußderEinführungzweier Bisarylphosphino-Gruppen mit unterschiedlichen Elektronendichten and den Phosphoratomen auf die optische Induktion。II

  摘要：

  通过引入两个双-芳基膦基[（4-X-苯基）2 P-和（4-Y-苯基）2 P-；（R，R）-Diop进行修饰。在磷原子上具有不同电荷密度的X，Y不同取代基]，从而形成不对称取代的diop衍生物。在α-酰基氨基丙烯酸乙酯（AAEE）和（Z）-α-酰基氨基肉桂酸甲酯（AZME）加[Rh]加氢的基础上，研究了取代基的影响和2倍旋转轴的损失。（不对称取代的Diop导数）（COD）] + BF 4 −（ns-Rh）作为具有取代基空间影响最小的催化前体。我们最近报道的相同底物的氢化的结果，但用的[Rh（对称取代迪奥普衍生物）（COD）] + BF 4 - （S-的Rh）作为催化剂前体。我们通过s-Rh（1）的氢化实验发现的取代基的电子和空间效应影响了ns-Rh的光学收率，而ns-Rh几乎相加。这意味着用ns-Rh获得的光学产率与通过平均相应s-Rh的光学产率计算出的值相当一致。令人惊讶的是，取代基的电子

  DOI：

  10.1016/0022-328x(89)87036-6
• 作为产物：
  描述：

  二苯基膦酸锂 以 四氢呋喃 为溶剂， 生成 (4R,5R)-4-diphenylphosphinomethyl-5-bis(4-N,N-dimethylaminophenyl)phosphinomethyl-2,2-dimethyl-1,3-dioxolane
  参考文献：
  名称：

  Catalytic asymmetric hydrogenation with rhodium complexes of improved DIOPS bearing para-dimethylamino group on the basis of our designing concept

  摘要：

  DOI：

  10.1016/s0040-4039(00)80599-7

文献信息

• Asymmetric Reactions Catalyzed by Chiral Metal Complexes. LVII. Synthesis of Efficient Chiral Bisphosphine Ligands, Modified DIOPs, (4R,5R)-4-(Diaryl- or dialkylphosphino)methyl-5-(diarylphosphino)methyl-2,2-dimethyl-1,3-dioxolanes, and Their Use in Rhodium(I)-Catalyzed Asymmetric Hydrogenations.
  作者：Toshiaki MORIMOTO、Mitsuo CHIBA、Kazuo ACHIWA

  DOI：10.1248/cpb.41.1149

  日期：——

  Modified DIOPs, (4R, 5R)-4-(diaryl- or dialkylphosphino)methyl-5-(diarylphosphino)methyl-2, 2-dimethyl-1, 3-dioxolanes, were prepared on the basis of our design concept, and used as ligands for the rhodium(I)-catalyzed asymmetric hydrogenations of ketopantolactone, itaconic acid, demethyl itaconate, and β-aryl-substituted itaconic acid derivatives. A neutral rhodium(I)-complex of (4R-trans)-dicyclohexyl[[5-[(diphenylphosphino)methyl]-2, 2-dimethyl-1, 3-dioxolan-4-yl]methyl]phosphine (DIOCP) bearing both a dicyclohexylphosphino group and a diphenylphosphino group was found to be a more efficient catalyst than the original DIOP in the asymmetric hydrogenation of ketopantolactone. Modified DIOPs bearing electron-donating groups at their para positions were efficient ligands for the rhodium(I)-catalyzed asymmetric hydrogenations of itaconic acid and its derivatives; in particular, (4R-trans)-[(2, 2-dimethyl-1, 3-dioxolane-4, 5-diyl)bis(metylene)]bis[bis(4'-methoxy-3', 5'-dimethylphenyl)phosphine] (MOD-DIOP) bearing both a p-methoxy group and two m, m'-methyl groups on each phenyl group showed much higher enantioselectivity and catalytic activity than DIOP.

  改良的DIOPs，(4R, 5R)-4-(二芳基或二烷基磷酰基)甲基-5-(二芳基磷酰基)甲基-2, 2-二甲基-1, 3-二噁烷，基于我们的设计概念制备，并用作铑(I)催化的酮平滑酸、丁烯二酸、去甲基丁烯二酸酯和β-芳基取代丁烯二酸衍生物的不对称氢化的配体。含有二环己基磷酰基和二苯基磷酰基的(4R-trans)-二环己基[[5-[(二苯基磷酰基)甲基]-2, 2-二甲基-1, 3-二噁烷-4-基]甲基]磷酸盐（DIOCP）被发现是比原始DIOP在酮平滑酸的不对称氢化反应中更有效的催化剂。具有电子给体基团的改良DIOPs在其对位上是铑(I)催化的丁烯二酸及其衍生物不对称氢化的有效配体；特别是，(4R-trans)-[(2, 2-二甲基-1, 3-二噁烷-4, 5-双基)双(亚甲基)]双[双(4'-甲氧基-3', 5'-二甲基苯)磷]（MOD-DIOP）同时具有p-甲氧基基团和每个苯基上的两个m, m'-甲基基团，其对映选择性和催化活性显著高于DIOP。
• MORIMOTO, TOSHIAKI;CHIBA, MITSUO;ACHIWA, KAZUO, TETRAHEDRON LETT., 29,(1988) N 37, C. 4755-4758
  作者：MORIMOTO, TOSHIAKI、CHIBA, MITSUO、ACHIWA, KAZUO

  DOI：——

  日期：——