(R)-(-)-2-(dimethylamino)-2'-(diphenylphosphino)-1,1'-binaphthyl

• 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: (R)-(-)-2-(dimethylamino)-2'-(diphenylphosphino)-1,1'-binaphthyl
• 英文别名: 1-(2-diphenylphosphanylnaphthalen-1-yl)-N,N-dimethylnaphthalen-2-amine
• 化学式: C₃₄H₂₈NP
• 分子量: 481.577
• InChiKey: VJCICCSVPBEHDK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.9
• 重原子数：
  36
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-(-)-2-(dimethylamino)-2'-(diphenylphosphino)-1,1'-binaphthyl 在 air 作用下， 以 四氢呋喃 为溶剂， 反应 10.0h， 以62%的产率得到(R)-(-)-2-dimethylamino-2'-diphenylphosphinyl-1,1'-binaphthyl
  参考文献：
  名称：

  Derivatives of 2-Amino-2‘-diphenylphosphino-1,1‘-binaphthyl (MAP) and Their Application in Asymmetric Palladium(0)-Catalyzed Allylic Substitution

  摘要：

  (R)-(+)-2-Amino-2'-hydroxy-1,1'-binaphthyl (NOBIN, 5) can be readily converted into a series of novel N,N-disubstituted aminophosphines 9 and 23-25. The N,N-dimethyl derivative (R)-9 (MAP) was prepared via a sequence involving reductive alkylation with CH2O and NaBH4 (5 --> 6), Pd-(O)-catalyzed coupling of the corresponding triflate with Ph2P(O)H (7 --> 8), and reduction of the resulting phosphine oxide with Cl3SiH (8 --> 9). Variation of this scheme was required for the preparation of 23-25 as the phosphinylation failed in the presence of bulky N substituents; the N-protected triflate 17 was first coupled with Ph2P(O)H, and the resulting phosphine oxide 18 was reduced with Cl3SiH to give the aminophosphine 19, which was then subjected to reductive alkylation with individual ketones and NaBH4. The new P,N-binaphthyls thus obtained (23-25 and 9) were utilized as chiral ligands in Pd(O)-catalyzed allylic substitution. The enantioselectivites obtained for racemic 1,3-diphenylprop-2-en-1-yl acetate (+/-)-26 and malonate nucleophiles, which gave (S)-(-28, (R)-(+)-29, and (R)-(+)-30 as the respective products tin up to 71-73% ee at room temperature with Cs2CO3 in CH2Cl2 and 9 or 23 as a ligand), are interpreted in terms of the chelated transition state 37 and preferential attack at the allylic terminus that is trans with respect to the phosphorus acceptor atom.

  DOI：

  10.1021/jo980757x
• 作为产物：
  描述：

  (R)-(-)-2-dimethylamino-2'-diphenylphosphinyl-1,1'-binaphthyl 在 三氯硅烷 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 18.0h， 以90%的产率得到(R)-(-)-2-(dimethylamino)-2'-(diphenylphosphino)-1,1'-binaphthyl
  参考文献：
  名称：

  通过用 2-三甲基甲硅烷氧基呋喃取代 Morita-Baylis-Hillman 乙酸盐，手性膦催化对映选择性构建 γ-丁烯内酯

  摘要：

  手性多功能膦 (R)-N-(2'-二苯基膦酰基-[1,1']联萘基-2-基)甲磺酰胺 L2 或 (R)-N-(2'-二苯基膦酰基-[1,1']联萘基- 2-基）乙酰胺 L3 是 MBH 乙酸酯 1 与 2-三甲基甲硅烷氧基呋喃 2 烯丙基取代的有效催化剂，以在水存在下以良好至极好的产率和对映体过量提供 γ-丁烯内酯 3。

  DOI：

  10.1021/ja802422d
• 作为试剂：
  描述：

  甲基丙二酸二甲酯 、 乙酸肉桂酯 在 sodium hydride 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 、 (R)-(-)-2-(dimethylamino)-2'-(diphenylphosphino)-1,1'-binaphthyl 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以96%的产率得到2-methyl-2-(3-phenyl-2-propenyl)malonic acid dimethyl ester
  参考文献：
  名称：

  Derivatives of 2-Amino-2‘-diphenylphosphino-1,1‘-binaphthyl (MAP) and Their Application in Asymmetric Palladium(0)-Catalyzed Allylic Substitution

  摘要：

  (R)-(+)-2-Amino-2'-hydroxy-1,1'-binaphthyl (NOBIN, 5) can be readily converted into a series of novel N,N-disubstituted aminophosphines 9 and 23-25. The N,N-dimethyl derivative (R)-9 (MAP) was prepared via a sequence involving reductive alkylation with CH2O and NaBH4 (5 --> 6), Pd-(O)-catalyzed coupling of the corresponding triflate with Ph2P(O)H (7 --> 8), and reduction of the resulting phosphine oxide with Cl3SiH (8 --> 9). Variation of this scheme was required for the preparation of 23-25 as the phosphinylation failed in the presence of bulky N substituents; the N-protected triflate 17 was first coupled with Ph2P(O)H, and the resulting phosphine oxide 18 was reduced with Cl3SiH to give the aminophosphine 19, which was then subjected to reductive alkylation with individual ketones and NaBH4. The new P,N-binaphthyls thus obtained (23-25 and 9) were utilized as chiral ligands in Pd(O)-catalyzed allylic substitution. The enantioselectivites obtained for racemic 1,3-diphenylprop-2-en-1-yl acetate (+/-)-26 and malonate nucleophiles, which gave (S)-(-28, (R)-(+)-29, and (R)-(+)-30 as the respective products tin up to 71-73% ee at room temperature with Cs2CO3 in CH2Cl2 and 9 or 23 as a ligand), are interpreted in terms of the chelated transition state 37 and preferential attack at the allylic terminus that is trans with respect to the phosphorus acceptor atom.

  DOI：

  10.1021/jo980757x

文献信息

• Ligands for metals and improved metal-catalyzed processes based thereon
  申请人：Massachusetts Institute of Technology

  公开号：US06307087B1

  公开（公告）日：2001-10-23

  One aspect of the present invention relates to novel ligands for transition metals. A second aspect of the present invention relates to the use of catalysts comprising these ligands in transition metal-catalyzed carbon-heteroatom and carbon-carbon bond-forming reactions. The subject methods provide improvements in many features of the transition metal-catalyzed reactions, including the range of suitable substrates, reaction conditions, and efficiency.

  本发明的一个方面涉及用于过渡金属的新颖配体。本发明的第二个方面涉及在过渡金属催化的碳-杂原子和碳-碳键形成反应中使用含有这些配体的催化剂。本方法在许多过渡金属催化反应的特征上提供了改进，包括适宜的底物范围、反应条件和效率。
• Catalytic Asymmetric Vinylation of Ketone Enolates
  作者：André Chieffi、Ken Kamikawa、Jens Åhman、Joseph M. Fox、Stephen L. Buchwald

  DOI：10.1021/ol0159470

  日期：2001.6.1

  [see reaction]. A protocol for the catalytic asymmetric vinylation of ketone enolates has been developed. Key to the success of this process was the development of new electron-rich chiral monodentate ligands.

  [请参阅反应]。已开发出一种用于酮烯醇酯催化不对称乙烯基化的方案。该方法成功的关键是开发新的富含电子的手性单齿配体。
• [EN] BIARYL LIGANDS<br/>[FR] LIGANDS BIARYLE
  申请人：UNIV FLORIDA

  公开号：WO2015038872A1

  公开（公告）日：2015-03-19

  Embodiments of the present disclosure provide for biaryl ligands (also referred to herein as "biaryl compound"), biaryl complexes, methods of making biaryl compounds, methods of making single enantiomers of these biaryl compounds, methods of use (e.g., catalysis) and the like.

  本公开的实施例提供了联苯配体（在本文中也称为“联苯化合物”）、联苯配合物的制备方法、制备这些联苯化合物的单对映体的方法、使用方法（例如催化）等。
• Efficient synthesis of optically active 2-amino-2'-diphenylphosphino-1,1'-binaphthyl and its derivatives
  作者：Kenzo Sumi、Takao Ikariya、Ryoji Noyori

  DOI：10.1139/v99-248

  日期：2000.6.1

  Optically active 2-amino-2'-diphenylphosphino-1,1'-binaphthyls having various functional groups, such as amino, alkoxycarbonylamino, acylamino, mono- and dialkylamino, and sulfonylamino at C2 position were prepared. The key intermediate of the above aminophosphines was 2-carbamoyl-2'-diphenylphosphinyl-1,1'-binaphthyl synthesized from optically active 2-cyano-2'-diphenylphosphinyl-1,1'-binaphthyl. The transformation of the carbamoyl group to an amino group was effected by the Hofmann reaction.Key words: aminophosphine ligand, Hofmann reaction, optically active phosphine ligand.

  具有各种官能团的具有光学活性的2-氨基-2'-二苯基磷酰基-1,1'-联萘，例如氨基，烷氧羰基氨基，酰胺基，单烷基和双烷基氨基，以及C2位置的磺酰胺基被制备。上述氨基磷酸酯的关键中间体是由具有光学活性的2-氰基-2'-二苯基磷酰基-1,1'-联萘合成的2-氨基甲酰基-2'-二苯基磷酰基-1,1'-联萘。将甲酰基转化为氨基是通过Hofmann反应实现的。关键词：氨基磷酸酯配体，Hofmann反应，光学活性磷酸酯配体。
• Backbone Effect of MAP Ligands on Their Coordination Patterns with Palladium(II)
  作者：Yi Wang、Xin Li、Jie Sun、Kuiling Ding

  DOI：10.1021/om020475u

  日期：2003.4.1

  and (R)-5 of chiral P, N auxiliaries (R)-1 and (R)-3 have been prepared. The X-ray structures of the complexes have been determined, and the results clearly show that two different chelating modes (P, N vs P, Cσ) are involved. The coordination patterns of donating atoms were dependent on the binaphthyl backbone of the chiral ligands. The isodesymmetrization revealed that the reaction occurs without

  已经制备了手性P，N助剂（R）-1和（R）-3的烯丙基钯配合物（R）-4和（R）-5。确定了配合物的X射线结构，结果清楚地表明了两种不同的螯合模式（P，N与P，Cσ）参与其中。供体原子的配位方式取决于手性配体的联萘骨架。异构化表明反应没有区域化学记忆效应发生，这表明在亲核攻击之前已经达到了完全的动态平衡。这些结果，与NMR研究揭示的配合物的溶液行为相结合，提供了对它们在丙二酸二甲酯中的1,3-二苯基丙-2-烯-1-基乙酸酯的烯丙基取代中的不对称诱导的进一步理解。对映体选择性的急剧增强与（[R ）- 3作为手性诱导剂可以与催化剂的不同的螯合模式（[R ）- 5从（的[R ） -4。在配合物（R）-4和（R）-5中，两个钯供体的咬合角变化被认为是其催化对映选择性显着不同的直接原因。