(+/-)-8-bromo-2'-methoxy-1,1'-binaphthyl | 504406-31-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (+/-)-8-bromo-2'-methoxy-1,1'-binaphthyl
• 英文别名: 8'-Bromo-2-methoxy-1,1'-binaphthalene；1-bromo-8-(2-methoxynaphthalen-1-yl)naphthalene
• CAS: 504406-31-9
• 化学式: C₂₁H₁₅BrO
• 分子量: 363.253
• InChiKey: XZHNTLOKPXDXCM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-8-bromo-2'-methoxy-1,1'-binaphthyl 在 [Pd(dibenzylideneacetone)2] 盐酸 、 双(2-二苯基磷苯基)醚 、 sodium t-butanolate 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 24.0h， 生成 (+/-)-8-amino-2'-methoxy-1,1'-binaphthyl
  参考文献：
  名称：

  2,8′-Disubstituted-1,1′-Binaphthyls: A New Pattern in Chiral Ligands

  摘要：

  The title binaphthyls 19 and 26, which are the positional isomers of 2-methoxy-2'-(diphenylphosphino)-1,1'-binaphthyl (MOP, 19) and 2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN, 26), have been synthesized by Suzuki coupling as the key step (10 + 15 --> 18), followed by functional group transformations, involving C-P and C-N bond formation (18 --> 19 and 18 --> 23). Racemic intermediate 22 was resolved by co-crystallization with N-benzylcinchonidinium chloride and the absolute configuration determined by X-ray crystallography. These novel binaphthyls are configurationally stable and, as such, potentially usable as chiral ligands in asymmetric reactions. Michael addition of the glycine-derived enolate 40 to methyl acrylate, carried out in the presence of (R)-(-)-27 as the chiral phase-transfer catalyst, afforded L-glutamic acid (S)-(+)-43 of 92% ee (after hydrolysis of the primary product).

  DOI：

  10.1002/1521-3765(20021018)8:20<4633::aid-chem4633>3.0.co;2-n
• 作为产物：
  描述：

  1,8-二氨基萘 在 四(三苯基膦)钯 硫酸 、 sodium carbonate 、 溶剂黄146 、 sodium nitrite 作用下， 以 乙二醇二甲醚 为溶剂， 反应 42.5h， 生成 (+/-)-8-bromo-2'-methoxy-1,1'-binaphthyl
  参考文献：
  名称：

  2,8′-Disubstituted-1,1′-Binaphthyls: A New Pattern in Chiral Ligands

  摘要：

  The title binaphthyls 19 and 26, which are the positional isomers of 2-methoxy-2'-(diphenylphosphino)-1,1'-binaphthyl (MOP, 19) and 2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN, 26), have been synthesized by Suzuki coupling as the key step (10 + 15 --> 18), followed by functional group transformations, involving C-P and C-N bond formation (18 --> 19 and 18 --> 23). Racemic intermediate 22 was resolved by co-crystallization with N-benzylcinchonidinium chloride and the absolute configuration determined by X-ray crystallography. These novel binaphthyls are configurationally stable and, as such, potentially usable as chiral ligands in asymmetric reactions. Michael addition of the glycine-derived enolate 40 to methyl acrylate, carried out in the presence of (R)-(-)-27 as the chiral phase-transfer catalyst, afforded L-glutamic acid (S)-(+)-43 of 92% ee (after hydrolysis of the primary product).

  DOI：

  10.1002/1521-3765(20021018)8:20<4633::aid-chem4633>3.0.co;2-n

文献信息

• Synthesis of 2-Hydroxy-8'-(hydroxymethyl)-1,1'-binaphthalene (iso-Homo-BINOL). A New Structural Pattern in the Binaphthyl Realm
  作者：Štěpán Vyskočil、Stephen C. Lockhart、William L. Mitchell、Pavel Kočovský

  DOI：10.1135/cccc20030907

  日期：——

  The title compound 7 has been synthesized in a racemic form, using Suzuki coupling (8 + 15 → 16) as the key step. Pure enantiomer (S)-(-)-7 has been obtained by carbonylation of the known bromide (S)-(+)-12 followed by reduction of the resulting methyl ester (S)-(+)-18 with LiAlH₄.

  标题化合物7已经以外消旋形式合成，使用Suzuki偶联（8 + 15 → 16）作为关键步骤。通过对已知溴化物（S）-(+)-12的羰基化，然后用LiAlH4还原所得的甲酸甲酯（S）-(+)-18，得到了纯对映体（S）-(-)-7。
• 2,8′-Disubstituted-1,1′-Binaphthyls: A New Pattern in Chiral Ligands
  作者：Štěpán Vyskočil、Luděk Meca、Iva Tišlerová、Ivana Císařová、Miroslav Polášek、Syuzanna R. Harutyunyan、Yuri N. Belokon、Russel M. J. Stead、Louis Farrugia、Stephen C. Lockhart、William L. Mitchell、Pavel Kočovský

  DOI：10.1002/1521-3765(20021018)8:20<4633::aid-chem4633>3.0.co;2-n

  日期：2002.10.18

  The title binaphthyls 19 and 26, which are the positional isomers of 2-methoxy-2'-(diphenylphosphino)-1,1'-binaphthyl (MOP, 19) and 2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN, 26), have been synthesized by Suzuki coupling as the key step (10 + 15 --> 18), followed by functional group transformations, involving C-P and C-N bond formation (18 --> 19 and 18 --> 23). Racemic intermediate 22 was resolved by co-crystallization with N-benzylcinchonidinium chloride and the absolute configuration determined by X-ray crystallography. These novel binaphthyls are configurationally stable and, as such, potentially usable as chiral ligands in asymmetric reactions. Michael addition of the glycine-derived enolate 40 to methyl acrylate, carried out in the presence of (R)-(-)-27 as the chiral phase-transfer catalyst, afforded L-glutamic acid (S)-(+)-43 of 92% ee (after hydrolysis of the primary product).