(S)-(-)-N-(2,2-dimethylpropionyl)-2-<(diphenylphosphino)methyl>pyrrolidine | 145818-29-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (S)-(-)-N-(2,2-dimethylpropionyl)-2-<(diphenylphosphino)methyl>pyrrolidine
• 英文别名: (S)-1-{2-[(diphenylphosphino)methyl]pyrrolidin-1-yl}-2,2-dimethylpropan-1-one；(S)-1-{2-[(diphenylphosphino)methyl]pyrrolidinyl}-2,2-dimethylpropan-1-one；(S)-(-)-1-(2,2-dimethylpropionyl)-2-(diphenylphosphinomethyl)-pyrrolidine；amidomonophosphine；1-[(2S)-2-(diphenylphosphanylmethyl)pyrrolidin-1-yl]-2,2-dimethylpropan-1-one
• CAS: 145818-29-7
• 化学式: C₂₂H₂₈NOP
• 分子量: 353.444
• InChiKey: YUFICFYMFGQYMU-SFHVURJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-(-)-N-(2,2-dimethylpropionyl)-2-<(diphenylphosphino)methyl>pyrrolidine 在 dimethyl sulfide borane 、 镍 、 二乙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 8.0h， 以81%的产率得到(S)-(-)-1-(2,2-dimethyl)propyl-2-(diphenylphosphinomethyl)-pyrrolidine
  参考文献：
  名称：

  Unsymmetrical terdentate phosphorus-nitrogen-nitrogen (PNN) ligands: effect of the M/L ratio and the pendant group on stereoselectivity

  摘要：

  Twelve novel, unsymmetrical terdentate pyrrolidine-based phosphorus-nitrogen ligands were prepared. These ligands promoted very high catalytic activity in the palladium-catalysed allylic substitution reactions of 1,3-diphenylpropenyl acetate with malonate esters (100% conversion at 0degreesC in <2 h). Enantioselectivities up to 94% were attained. An unusual effect of metal-to-ligand ratio was observed. Various structural features affecting the enantioselectivity and stereoinduction were examined and discussed. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00361-6
• 作为产物：
  描述：

  (S)-2-(甲苯磺酰氧基甲基)吡咯烷-1-甲酸叔丁酯 在 sodium 、 三乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 11.5h， 生成 (S)-(-)-N-(2,2-dimethylpropionyl)-2-<(diphenylphosphino)methyl>pyrrolidine
  参考文献：
  名称：

  格氏试剂对环状α，β-不饱和羰基化合物的催化对映选择性共轭加成

  摘要：

  由铜盐，手性膦和格氏试剂与环己烯酮产生的有机铜试剂的催化不对称共轭加成反应高度依赖于铜离子，溶剂，格氏试剂和手性膦结构的抗衡阴离子。在-78°C下，使用8摩尔％的碘化铜，32摩尔％的氨基膦3和1.2当量的有机氯化镁与环己烯酮在乙醚中的混合物进行反应，得到3-取代的环己酮，其ee最高为92％，ee为90 ％ 屈服。

  DOI：

  10.1016/s0040-4020(99)00095-2
• 作为试剂：
  描述：

  乙基溴化镁 、 肉桂基溴 在 tetrakis(acetonitrile)copper(I)tetrafluoroborate 、 (S)-(-)-N-(2,2-dimethylpropionyl)-2-<(diphenylphosphino)methyl>pyrrolidine 作用下， 以 二氯甲烷 、 乙醚 为溶剂， 生成 1-pentenylbenzene 、 (R)-3-phenyl-1-pentene
  参考文献：
  名称：

  用芳基和乙基格氏试剂进行铜催化的不对称烯丙基取代。

  摘要：

  苯基和乙基镁溴化物在手性酰胺基膦-铜（I）配合物的催化下，具有对映选择性高的区域选择性不对称烯丙基取代。

  DOI：

  10.1039/b809140d

文献信息

• Hemilabile Amidomonophosphine Ligand−Rhodium(I) Complex-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to Cycloalkenones
  作者：Masami Kuriyama、Kazushige Nagai、Ken-ichi Yamada、Yoshinao Miwa、Tooru Taga、Kiyoshi Tomioka

  DOI：10.1021/ja0261933

  日期：2002.7.1

  contains a hard donor site in addition to the soft donor in a molecule. Phosphorus atom strongly bonds to rhodium(I), and the amide carbonyl oxygen is coordinatively labile. The reaction efficacy of phenylboronic acid with cyclopent-2-en-1-one was significantly dependent on the possibility of coordination of the amide carbonyl oxygen to rhodium(I).

  芳基硼酸与环烯酮的不对称 1,4-加成反应由 1 mol% 的氨基单膦-铑 (I) 催化剂在 1,4-二恶烷和水的 10:1 混合物中于 100 摄氏度催化，得到 3-芳基环烷酮具有相当高的对映选择性和高产率。核磁共振、红外光谱和 X 射线光谱表明，这种双齿氨基单膦表现为半稳定配体，除了分子中的软供体外，还包含硬供体位点。磷原子与铑 (I) 紧密结合，酰胺羰基氧配位不稳定。苯基硼酸与 cyclopent-2-en-1-one 的反应效率显着取决于酰胺羰基氧与铑 (I) 配位的可能性。
• Proline-Based P,O Ligand/Iridium Complexes as Highly Selective Catalysts: Asymmetric Hydrogenation of Trisubstituted Alkenes
  作者：Denise Rageot、David H. Woodmansee、Benoît Pugin、Andreas Pfaltz

  DOI：10.1002/anie.201104105

  日期：2011.10.4

  O joins the mix: P,O ligands (L1) form efficient iridium catalysts for the asymmetric hydrogenation of olefins. The proline‐derived ligands lead to high enantioselectivities with several classes of alkenes, most notably with α,β‐unsaturated carboxylic esters and ketones, where they match or even surpass the ee values reported for the best N,P and C,N ligands.

  P，O加入混合物：P，O配体（L1）形成有效的铱催化剂，用于烯烃的不对称加氢。脯氨酸衍生的配体对几种烯烃具有很高的对映选择性，最显着的是与α，β-不饱和羧酸酯和酮匹配，甚至超过了 报道的最佳N，P和C，N配体的ee值。
• Catalytic enantioselective conjugate addition of Grignard reagents to cyclic α,β-unsaturated carbonyl compounds
  作者：Motomu Kanai、Yuichi Nakagawa、Kiyoshi Tomioka

  DOI：10.1016/s0040-4020(99)00095-2

  日期：1999.3

  A catalytic asymmetric conjugate addition reaction of organocopper reagents, generated from copper salt, a chiral phosphine, and Grignard reagent, with cyclohexenone is highly dependent on the counter anion of copper species, solvents, Grignard reagents, and the structure of the chiral phosphine. The reaction using the combination of 8 mol% of copper iodide, 32 mol% of the amidophosphine 3, and 1.2

  由铜盐，手性膦和格氏试剂与环己烯酮产生的有机铜试剂的催化不对称共轭加成反应高度依赖于铜离子，溶剂，格氏试剂和手性膦结构的抗衡阴离子。在-78°C下，使用8摩尔％的碘化铜，32摩尔％的氨基膦3和1.2当量的有机氯化镁与环己烯酮在乙醚中的混合物进行反应，得到3-取代的环己酮，其ee最高为92％，ee为90 ％ 屈服。
• Solvent effect and NMR behaviour in a chiral amidophosphine mediated reaction of organocuprate with chalcone
  作者：Motomu Kanai、Kenji Koga、Kiyoshi Tomioka

  DOI：10.1039/c39930001248

  日期：——

  A dramatic reversal in the direction of enantiofacial differentiation has been observed in a chiral phosphine mediated reaction of organocuprate with chalcone providing S- and R-products in diethyl ether and tetrahydrofuran (THF), respectively, and correlated with the pattern of coordination.

  在有机铜与查尔酮的手性膦反应中，对映异构的方向发生了戏剧性的逆转，分别在乙醚和四氢呋喃（THF）中产生了S-和R-产物，这与配位模式有关。
• Unsymmetrical terdentate phosphorus-nitrogen-nitrogen (PNN) ligands: effect of the M/L ratio and the pendant group on stereoselectivity
  作者：Xiaohui Cheng、King Kuok (Mimi) Hii

  DOI：10.1016/s0957-4166(03)00361-6

  日期：2003.7

  Twelve novel, unsymmetrical terdentate pyrrolidine-based phosphorus-nitrogen ligands were prepared. These ligands promoted very high catalytic activity in the palladium-catalysed allylic substitution reactions of 1,3-diphenylpropenyl acetate with malonate esters (100% conversion at 0degreesC in <2 h). Enantioselectivities up to 94% were attained. An unusual effect of metal-to-ligand ratio was observed. Various structural features affecting the enantioselectivity and stereoinduction were examined and discussed. (C) 2003 Elsevier Ltd. All rights reserved.