(R)-(+)-2-<(2"-adamantyl)amino>-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-<(2"-adamantyl)amino>-2'-hydroxy-1,1'-binaphthyl
• 英文别名: 1-[2-(2-Adamantylamino)naphthalen-1-yl]naphthalen-2-ol
• 化学式: C₃₀H₂₉NO
• 分子量: 419.566
• InChiKey: VCEGSNARILDACT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  32
• 可旋转键数：
  3
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.33
• 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-<(2"-adamantyl)amino>-2'-hydroxy-1,1'-binaphthyl 在 六甲基磷酰三胺 、 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-[(2-adamantyl)amino]-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：

  金刚烷酮 、 (S)-(+)-2-氨基-2'-羟基-1,1'-联萘 在 sodium tetrahydroborate 、 硫酸 作用下， 以 四氢呋喃 为溶剂， 反应 0.25h， 以57%的产率得到(R)-(+)-2-<(2"-adamantyl)amino>-2'-hydroxy-1,1'-binaphthyl
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo9807565

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.
• 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.