(R)-(+)-2-(cyclohexylamino)-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-(cyclohexylamino)-2'-hydroxy-1,1'-binaphthyl
• 英文别名: (R)-2'-(cyclohexylamino)-[1,1'-binaphthalen]-2-ol；(R)-2'-(cyclohexylamino)-[1,1'-binaphthyl]-2-ol；1-[2-(Cyclohexylamino)naphthalen-1-yl]naphthalen-2-ol
• 化学式: C₂₆H₂₅NO
• 分子量: 367.491
• InChiKey: REYWATOJPXJGSK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  28
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  32.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-(+)-2-(cyclohexylamino)-2'-hydroxy-1,1'-binaphthyl 在 N,N-二甲基丙烯基脲 、 正丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.67h， 生成 (R_a)-2-cyclohexylamino-2'-(2-phenylpropanoyloxy)-1,1'-binaphthyl
  参考文献：
  名称：

  Asymmetric α-Alkylation of Phenylacetates Using 2-Alkylamino-2′-hydroxy-1,1′-binaphthyls as Chiral Auxiliaries

  摘要：

  alpha-Alkylation of 2-phenylacetate ester of 2-alkylamino-2'-hydroxy- 1, 1'-binaphthyls with various alkyl iodides proceeded with good stereoselectivities. An intramolecular hydrogen bonding between N-H group and the carbonyl oxygen seemed to play an important role for asymmetric induction. The auxiliary was also applicable to Diels-Alder reaction of an acrylate.

  DOI：

  10.1080/10242430215713
• 作为产物：
  描述：

  环己胺 在 potassium carbonate 、 三乙胺 、 potassium iodide 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 28.5h， 生成 (R)-(+)-2-(cyclohexylamino)-2'-hydroxy-1,1'-binaphthyl
  参考文献：
  名称：

  对映选择性的O-芳基胺化反应的可切换笑容重排

  摘要：

  由丰富且容易获得的前体组成的对映异构体苯胺的不对称组装是有机合成中最具挑战性但最有价值的过程之一。使用高效的Smiles重排完成O-芳烃的可切换对映选择性胺化反应，可得到非对称的2'-氨基[1,1'-双萘] -2-ol（即NOBIN型）和[1,1' -双萘] -2,2'-二胺（即BINAM型）衍生物。这种无过渡金属的策略提供了一种强大的途径，可以访问各种先进的高度功能化的对映体丰富的苯胺。

  DOI：

  10.1021/acs.orglett.9b01848

文献信息

• 一类手性芳香胺类化合物及其制备方法
  申请人：中国科学技术大学

  公开号：CN107814729B

  公开（公告）日：2019-11-22

  本发明公开了一类手性芳香胺类化合物及其制备方法，特征是在碱性条件下，式1类化合物和式II类化合物反应：其中R1为苯基、甲基、甲氧基、乙氧基、异丙氧基、苄氧基；R2为甲基、乙基、丙基、丁基；R3为氢或甲基；R4为氢、苯基或甲基；R5为甲基、乙基、丙基、丁基、苄基、苯基；R6为氢或甲基；得到具有相应结构式的手性芳香胺类化合物或其对映体、消旋体、非对映异构体或同位素标记的相应产物芳香胺类化合物。采用本发明方法易制得高光学纯度(ee值>99％)的手性芳香胺类化合物，在生物活性、材料、手性配体和手性催化剂等领域具有广泛的应用。本发明为开发一类新型不对称催化反应的催化剂奠定了基础，具有经济实用性和工业应用前景。
• 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.
• Switchable Smiles Rearrangement for Enantioselective <i>O</i>-Aryl Amination
  作者：Xihao Chang、Qinglin Zhang、Chang Guo

  DOI：10.1021/acs.orglett.9b01848

  日期：2019.6.21

  atropisomeric anilines from abundant and readily available precursors is one of the most challenging but valuable processes in organic synthesis. The use of highly efficient Smiles rearrangement to accomplish switchable enantioselective amination reactions of O-arenes provides access to nonsymmetric 2′-amino[1,1′-binaphthalen]-2-ol (i.e., NOBIN-type) and [1,1′-binaphthalene]-2,2′-diamine (i.e., BINAM-type)

  由丰富且容易获得的前体组成的对映异构体苯胺的不对称组装是有机合成中最具挑战性但最有价值的过程之一。使用高效的Smiles重排完成O-芳烃的可切换对映选择性胺化反应，可得到非对称的2'-氨基[1,1'-双萘] -2-ol（即NOBIN型）和[1,1' -双萘] -2,2'-二胺（即BINAM型）衍生物。这种无过渡金属的策略提供了一种强大的途径，可以访问各种先进的高度功能化的对映体丰富的苯胺。
• Asymmetric α-Alkylation of Phenylacetates Using 2-Alkylamino-2′-hydroxy-1,1′-binaphthyls as Chiral Auxiliaries
  作者：Masato Kawamura、Takashi Kurahashi、Shinsaku Shiraishi、Kazuaki Kudo

  DOI：10.1080/10242430215713

  日期：2002.11.1

  alpha-Alkylation of 2-phenylacetate ester of 2-alkylamino-2'-hydroxy- 1, 1'-binaphthyls with various alkyl iodides proceeded with good stereoselectivities. An intramolecular hydrogen bonding between N-H group and the carbonyl oxygen seemed to play an important role for asymmetric induction. The auxiliary was also applicable to Diels-Alder reaction of an acrylate.