H-(R)-Bin-OEt

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: H-(R)-Bin-OEt
• 英文别名: Ethyl 13-aminopentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene-13-carboxylate；ethyl 13-aminopentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene-13-carboxylate
• 化学式: C₂₆H₂₃NO₂
• 分子量: 381.474
• InChiKey: UYFLUVRJWNEJFF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  29
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  52.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  H-(R)-Bin-OEt 在 sodium hydroxide 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 51.0h， 生成 Cbz-(±)-Bin-OH
  参考文献：
  名称：

  Novel α,α-disubstituted α-aminoacids with axial dissymmetry and their N- or C-protected derivatives

  摘要：

  Racemic as well as enantiomerically pure 1,1'-binaphthyl-substituted alpha-aminoisobutyric acid (Bin), a new chiral atropoisomeric alpha, alpha-disubstituted glycine, and its biphenyl analogue (Bip), have been prepared with good yields by bis-alkylation of a glycine tert-butyl ester Schiff base with 2,2'-bis(bromomethyl)-1, 1'-binaphthyl and 2,2'-bis(bromomethyl)-1,1'-biphenyl, respectively, under phase transfer conditions. The free aminoacids Bin and Bip, as well as their N-protected (Z, Boc, Fmoc) and/or C-protected (ethyl or tert-butyl esters) derivatives, useful for the incorporation of these new aminoacids into peptides, have been obtained. A slow interconversion between the two enantiomers of the Bip derivatives is generally observed in H-1 NMR at room temperature, with a rotational energy barrier of 59 kJ mol(-1). (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00009-8
• 作为产物：
  描述：

  4-{[1-(4-Chloro-phenyl)-meth-(E)-ylidene]-amino}-4,5-dihydro-3H-cyclohepta[2,1-a;3,4-a']dinaphthalene-4-carboxylic acid tert-butyl ester 在 盐酸 、 硫酸 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 101.0h， 生成 H-(R)-Bin-OEt
  参考文献：
  名称：

  Novel α,α-disubstituted α-aminoacids with axial dissymmetry and their N- or C-protected derivatives

  摘要：

  Racemic as well as enantiomerically pure 1,1'-binaphthyl-substituted alpha-aminoisobutyric acid (Bin), a new chiral atropoisomeric alpha, alpha-disubstituted glycine, and its biphenyl analogue (Bip), have been prepared with good yields by bis-alkylation of a glycine tert-butyl ester Schiff base with 2,2'-bis(bromomethyl)-1, 1'-binaphthyl and 2,2'-bis(bromomethyl)-1,1'-biphenyl, respectively, under phase transfer conditions. The free aminoacids Bin and Bip, as well as their N-protected (Z, Boc, Fmoc) and/or C-protected (ethyl or tert-butyl esters) derivatives, useful for the incorporation of these new aminoacids into peptides, have been obtained. A slow interconversion between the two enantiomers of the Bip derivatives is generally observed in H-1 NMR at room temperature, with a rotational energy barrier of 59 kJ mol(-1). (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00009-8

文献信息

• Enantioselective fluorination of α-branched aldehydes and subsequent conversion to α-hydroxyacetals via stereospecific C–F bond cleavage
  作者：Kazutaka Shibatomi、Kazumasa Kitahara、Takuya Okimi、Yoshiyuki Abe、Seiji Iwasa

  DOI：10.1039/c5sc03486h

  日期：——

  The highly enantioselective fluorination of α-branched aldehydes was achieved using newly developed chiral primary amine catalyst.

  高度对映选择性氟化α-支链醛利用新开发的手性初级胺催化剂实现。
• Enantioselective decarboxylative protonation and deuteration of β-ketocarboxylic acids
  作者：Haruna Mizutani、Ryouta Kawanishi、Kazutaka Shibatomi

  DOI：10.1039/d1cc01610e

  日期：——

  Enantioselective decarboxylative protonation of tetralone-derived β-ketocarboxylic acids was achieved with up to 89% enantiomeric excess (ee)–in the presence of a chiral primary amine catalyst. Furthermore, this method was applied to enantioselective deuteration to afford the corresponding α-deuterioketones with up to 88% ee.

  的四氢萘酮衍生的β酮羧酸的对映选择性脱羧质子化用高达89％对映体过量（ee）实现-在手性伯胺催化剂的存在下进行。此外，将该方法应用于对映选择性氘化，以提供相应的 α-氘代酮，其 ee 高达 88%。
• Development of a New Chiral Spiro Oxazolinylpyridine Ligand (Spymox) for Asymmetric Catalysis
  作者：Kazutaka Shibatomi、Seiji Iwasa、Tsubasa Muto、Yusuke Sumikawa、Akira Narayama

  DOI：10.1055/s-0028-1087675

  日期：——

  A novel optically active 2-(oxazolinyl)pyridine ligand (Spymox)having a spiro binaphthyl backbone was synthesized from an α,α-disubstituted α-aminoacid (H-Bin-OH), and successfully used in palladium-catalyzed asymmetricallylic alkylations to afford the corresponding alkylated productswith 99% ee.

  由 α,α-二取代 α-氨基酸 (H-Bin-OH) 合成了具有螺联萘骨架的新型光学活性 2-(恶唑啉基)吡啶配体 (Spymox)，并成功用于钯催化的不对称烷基化反应中相应的烷基化产物具有 99% ee。
• JP2015/51967
  申请人：——

  公开号：——

  公开（公告）日：——
• Highly Enantioselective Chlorination of β-Keto Esters and Subsequent S_N2 Displacement of Tertiary Chlorides: A Flexible Method for the Construction of Quaternary Stereogenic Centers
  作者：Kazutaka Shibatomi、Yoshinori Soga、Akira Narayama、Ikuhide Fujisawa、Seiji Iwasa

  DOI：10.1021/ja304806j

  日期：2012.6.20

  Highly enantioselective chlorination of beta-oxo esters and subsequent stereospecific substitution of tertiary chlorides are described. Enantioselective chlorination of beta-keto esters and malonates was performed using a chiral Lewis acid catalyst prepared from Cu(OTf)(2) and the newly developed spirooxazoline ligand 2 to yield the desired a-chlorinated products with high enantioselectivity (up to 98% ee). Nucleophilic substitution of the resulting chlorides proceeded smoothly to afford a variety of chiral molecules such as alpha-amino, alpha-allcylthio, and alpha-fluoro esters, without loss of enantiopurity. The results of X-ray crystallographic analysis proved that Walden inversion occurs at the chlorinated tertiary carbon center. These results supported the fact that the substitution proceeds via an S(N)2 mechanism.