(E)-1-benzoyloxy-1-dimethylphosphonyl-1-butene | 241496-30-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-1-benzoyloxy-1-dimethylphosphonyl-1-butene
• 英文别名: (E)-1-benzoyloxy-1-dimethoxyphosphoryl-1-butene；[(E)-1-dimethoxyphosphorylbut-1-enyl] benzoate
• CAS: 241496-30-0
• 化学式: C₁₃H₁₇O₅P
• 分子量: 284.249
• InChiKey: NBIHLNDFAZJDLP-XYOKQWHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (E)-1-benzoyloxy-1-dimethylphosphonyl-1-butene 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 氢气 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、1.01 MPa 条件下， 反应 12.0h， 以99%的产率得到(R)-(-)-1-benzoyloxy-1-dimethylphosphonylbutane
  参考文献：
  名称：

  衍生自1-萘胺的新型手性膦-亚磷酰胺配体，用于高效的Rh催化不对称加氢

  摘要：

  由1-萘胺经两步转化制得一种新的手性膦-亚磷酰胺配体（S）-HY-Phos 1，并成功地应用于Rh催化的各种官能化烯烃的Rh催化不对称加氢反应中，包括α-（乙酰胺基）肉桂酸酯，烯酰胺和α-烯醇酯膦酸酯，分别达到了98％ee，99％ee和99％ee。

  DOI：

  10.1016/j.tetasy.2008.07.022
• 作为产物：
  描述：

  苯甲酸酐 、 Dimethyl (1-oxobutyl)phosphonate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 为溶剂， 反应 0.25h， 生成 (E)-1-benzoyloxy-1-dimethylphosphonyl-1-butene
  参考文献：
  名称：

  Enantioselective Synthesis of α-Hydroxy and α-Amino Phosphonates via Catalytic Asymmetric Hydrogenation

  摘要：

  [GRAPHICS]Cationic rhodium catalysts of the C-2 symmetric DuPHOS (1) and BPE (2) ligands have demonstrated the ability to asymmetrically hydrogenate a novel series of enol phosphonates (3) in good to excellent enantiomeric excess under mild conditions. Initial studies toward the catalytic asymmetric hydrogenation of enamido phosphonates (6 and 7) using the DuPHOS-Rh+ catalysts are also reported.

  DOI：

  10.1021/ol9906099

文献信息

• Tuning of the Structures of Chiral Phosphane-Phosphites: Application to the Highly Enantioselective Synthesis of α-Acyloxy Phosphonates by Catalytic Hydrogenation
  作者：Miguel Rubio、Sergio Vargas、Andrés Suárez、Eleuterio Álvarez、Antonio Pizzano

  DOI：10.1002/chem.200601032

  日期：2007.2.12

  ligands 1 and 5 in catalytic asymmetric hydrogenations of enol phosphonates 12 demonstrated a critical influence of the steric characteristics of the phosphane-phosphite in the course of the reaction, and optimization of the two phosphorus functionalities resulted in the production of versatile and efficient catalysts for this class of hydrogenations: enantioselectivities of up to 98% ee were thus obtained

  已经制备了一系列新的手性膦-亚磷酸酯5，并用于合成[Rh（cod）（5）] BF4（7）的铑配合物。在制备7中使用大的膦或亚磷酸酯基团避免了不希望的二取代的配合物的形成，其中一种已经被分离和表征了（9a）。配体5显示出与较大的膦亚磷酸酯1的重要区别：配合物7-不同于其刚性的[Rh（cod）（1）] BF4对应物-在溶液中显示了通量行为，与配位平面周围的骨架振动一致。在烯醇膦酸酯12的催化不对称氢化中对配体1和5的详细筛选表明，在反应过程中，膦亚磷酸酯的空间特征具有关键影响，两种磷官能团的优化以及对这类氢化反应的通用催化剂的生产：利用在β位带有烷基取代基的底物获得了高达98％ee的对映选择性，而对于具有挑战性的芳基对应物ee值高达92％。还研究了膦酸酯12a对Rh膦-亚磷酸酯片段的配位模式，并且观察到烯烃片段优先占据亚磷酸酯基团的顺式位置。从该观察结果也可以解释氢化膦酸酯的构型。因此，对于在
• Highly enantioselective hydrogenation of enol ester phosphonates catalyzed by rhodium phosphine-phosphite complexes
  作者：Miguel Rubio、Andrés Suárez、Eleuterio Álvarez、Antonio Pizzano

  DOI：10.1039/b414288h

  日期：——

  Chiral phosphine-phosphites provide versatile catalysts for the highly enantioselective hydrogenation of alpha-acyloxy alpha, beta-unsaturated phosphonates.

  手性膦-亚磷酸酯为α-酰氧基α，β-不饱和膦酸酯的高度对映选择性氢化提供了多种催化剂。
• Enantioselective Synthesis of α-Hydroxy and α-Amino Phosphonates via Catalytic Asymmetric Hydrogenation
  作者：Mark J. Burk、Timothy A. Stammers、Judith A. Straub

  DOI：10.1021/ol9906099

  日期：1999.8.1

  [GRAPHICS]Cationic rhodium catalysts of the C-2 symmetric DuPHOS (1) and BPE (2) ligands have demonstrated the ability to asymmetrically hydrogenate a novel series of enol phosphonates (3) in good to excellent enantiomeric excess under mild conditions. Initial studies toward the catalytic asymmetric hydrogenation of enamido phosphonates (6 and 7) using the DuPHOS-Rh+ catalysts are also reported.
• Readily Available Chiral Phosphine−Aminophosphine Ligands for Highly Efficient Rh-Catalyzed Asymmetric Hydrogenation of α-Enol Ester Phosphonates and α-Enamido Phosphonates
  作者：Dao-Yong Wang、Jia-Di Huang、Xiang-Ping Hu、Jun Deng、Sai-Bo Yu、Zheng-Chao Duan、Zhuo Zheng

  DOI：10.1021/jo702488j

  日期：2008.3.1

  [GRAPHICS]A new class of unsymmetrical hybrid phosphine-aminophosphine ligands has been prepared from commercially available, inexpensive (S)-1-phenylethylamine through a concise synthetic procedure. These ligands are not very sensitive to air and moisture, and displayed good enantioselectivities in the Rh-catalyzed asymmetric hydrogenation of various dimethyl alpha-benzoyloxyethenephosphonates bearing beta-aryl, beta-alkyl, and beta-alkoxy substituents and N-benzyloxycarbonyl alpha-enamido phosphonates, in which up to 97% ee was obtained. A side-by-side comparison study disclosed that these new phosphine-aminophosphine ligands showed better enantioselectivity than BoPhoz ligands.
• Highly Enantioselective Synthesis of α-Hydroxy Phosphonic Acid Derivatives by Rh-Catalyzed Asymmetric Hydrogenation with Phosphine–Phosphoramidite Ligands
  作者：Dao-Yong Wang、Xiang-Ping Hu、Jia-Di Huang、Jun Deng、Sai-Bo Yu、Zheng-Chao Duan、Xue-Feng Xu、Zhuo Zheng

  DOI：10.1002/anie.200702924

  日期：2007.10.15