(R)-(+)-2-(N-piperidinyl)-2'-hydroxy-1,1'-binaphthyl

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R)-(+)-2-(N-piperidinyl)-2'-hydroxy-1,1'-binaphthyl
• 英文别名: 1-(2-piperidin-1-ylnaphthalen-1-yl)naphthalen-2-ol
• 化学式: C₂₅H₂₃NO
• 分子量: 353.464
• InChiKey: RVIHFTOQVDIISS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  23.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  三氟甲磺酸酐 、 (R)-(+)-2-(N-piperidinyl)-2'-hydroxy-1,1'-binaphthyl 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以86%的产率得到(R)-(-)-2-(N-piperidinyl)-2'-(trifluoromethanesulfonyloxy)-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：

  2-萘酚 在 iron(III) chloride 、 二叔丁基过氧化物 、 三氟乙酸 作用下， 反应 44.0h， 生成 (R)-(+)-2-(N-piperidinyl)-2'-hydroxy-1,1'-binaphthyl
  参考文献：
  名称：

  FeCl 3催化苯酚与2-氨基萘的氧化交叉偶联的机理研究。

  摘要：

  研究了酚与伯，仲和叔2-氨基萘衍生物之间的选择性FeCl 3催化的氧化交叉偶联反应。这种可扩展方法的通用性为制备广泛用作配体和催化剂的N，O-联芳基化合物提供了一种可持续的选择。基于全面的动力学研究，提出了在关键的氧化偶联步骤中涉及三元配合物的催化循环，该三元配合物与偶联伙伴和氧化剂结合。此外，研究表明，该反应受环外酸碱和配体交换过程的调节。

  DOI：

  10.1021/acs.joc.0c00874

文献信息

• Synthesis of N-Alkylated and N-Arylated Derivatives of 2-Amino-2‘-hydroxy-1,1‘-binaphthyl (NOBIN) and 2,2‘-Diamino-1,1‘-binaphthyl and Their Application in the Enantioselective Addition of Diethylzinc to Aromatic Aldehydes
  作者：Štěpán Vyskočil、Stanislav Jaracz、Martin Smrčina、Martin Štícha、Vladimír Hanuš、Miroslav Polášek、Pavel Kočovský

  DOI：10.1021/jo9807565

  日期：1998.10.1

  High-yield reductive alkylation of(R)-(+)-1 and (R)-(+)-2 has been accomplished with a series of ketones (even as bulky as 2-adamantanone) and NaBH4/H2SO4 in THF at room temperature to give the respective N-alkylated binaphthyls 6a-c, 9a-c, and 10a-c. Related N-phenyl derivatives 14, 16, and 17 were obtained via the Pd(O)-catalyzed coupling of(R)-(+)-1 and (R)-(+)-2, respectively, with PhBr; no racemization was observed. Subsequent reductive methylation with CH2O and NaBH4/H2SO4 afforded the bidentate ligands 8a-c, 12a-c, 13a-c, 15, 18, and 19, which comprise a new class of binaphthyls. Their utility as chiral ligands has been demonstrated for the addition of Et2Zn to benzaldehyde and its congeners; the highest level of asymmetric induction was observed for N,N-dimethyl NOBIN (R)-(+)-3 (3 mol %) in conjunction with n-BuLi (5.4 mol %), which gave (R)-(+)-21a in 88% ee. Derivatives of the amino phenol 1 (NOBIN) proved more efficient than the corresponding diamines derived from 2. The stereochemical outcome and the enhancement of asymmetric induction by Li+ are discussed in terms of the chelated transition state 26.
• Derivatives of 2-Amino-2‘-diphenylphosphino-1,1‘-binaphthyl (MAP) and Their Application in Asymmetric Palladium(0)-Catalyzed Allylic Substitution
  作者：Štěpán Vyskočil、Martin Smrčina、Vladimír Hanuš、Miroslav Polášek、Pavel Kočovský

  DOI：10.1021/jo980757x

  日期：1998.10.1

  (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.
• Mechanistic Insights into the FeCl₃-Catalyzed Oxidative Cross-Coupling of Phenols with 2-Aminonaphthalenes
  作者：Vlada Vershinin、Hagit Forkosh、Mor Ben-Lulu、Anna Libman、Doron Pappo

  DOI：10.1021/acs.joc.0c00874

  日期：2021.1.1

  The selective FeCl3-catalyzed oxidative cross-coupling reaction between phenols and primary, secondary, and tertiary 2-aminonaphthalene derivatives was investigated. The generality of this scalable method provides a sustainable alternative for preparing N,O-biaryl compounds that are widely used as ligands and catalysts. Based on a comprehensive kinetic investigation, a catalytic cycle involving a ternary

  研究了酚与伯，仲和叔2-氨基萘衍生物之间的选择性FeCl 3催化的氧化交叉偶联反应。这种可扩展方法的通用性为制备广泛用作配体和催化剂的N，O-联芳基化合物提供了一种可持续的选择。基于全面的动力学研究，提出了在关键的氧化偶联步骤中涉及三元配合物的催化循环，该三元配合物与偶联伙伴和氧化剂结合。此外，研究表明，该反应受环外酸碱和配体交换过程的调节。