(S)-1-(α-aminobenzyl)-2-naphthol L-(+)-tartrate

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (S)-1-(α-aminobenzyl)-2-naphthol L-(+)-tartrate
• 英文别名: (S)-l-(α-aminobenzyl)-2-naphthol (R,R)-tartrate；(S)-(+)-1-(α-aminobenzyl)-2-naphthol tartrate；(S)-Betti base*(-)-tartaric acid；(S)-1-(Amino(phenyl)methyl)naphthalen-2-ol (2R,3R)-2,3-dihydroxysuccinate；1-[(S)-amino(phenyl)methyl]naphthalen-2-ol;(2R,3R)-2,3-dihydroxybutanedioic acid
• 化学式: C₄H₆O₆*C₁₇H₁₅NO
• 分子量: 399.4
• InChiKey: SFGQEHBXKVZEEH-YRSVLNEHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.47
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  161
• 氢给体数：
  6
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (S)-1-(α-aminobenzyl)-2-naphthol L-(+)-tartrate 在 sodium cyanoborohydride 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 (7aR,13S)-13-phenyl-8,9,10,11-tetrahydro-7aH,13H-naphtho[1,2-e]pyrido[2,1-b][1,3]oxazine
  参考文献：
  名称：

  Diastereopure Preparation of α-Benzotriazolyl 1-Azacycloalka[2,1-b][1,3]-oxazines and their Application as Versatile Chiral Precursors

  摘要：

  制备了一组非外消旋的贝蒂碱衍生的立体纯α-苯并三氮唑基1-氮杂环烷[2,1-b][1,3]恶嗪。这些化合物被用作制备手性配体和手性取代氮杂环化合物的前体，具有显著的立体选择性优势。

  DOI：

  10.1055/s-2003-43353
• 作为产物：
  描述：

  1-[氨基(苯基)甲基]-2-萘酚 在 硫酸 、 三乙胺 作用下， 以 水 、 丙酮 为溶剂， 反应 4.0h， 生成 (S)-1-(α-aminobenzyl)-2-naphthol L-(+)-tartrate
  参考文献：
  名称：

  An Efficient Kinetic Resolution of Racemic Betti Base Based on an Enantioselective N,O-Deketalization

  摘要：

  [GRAPHIC]An efficient kinetic resolution of racemic Betti base with L-(+)-tartaric acid in acetone was developed based on a novel enantioselective N,O-deketalization, by which the enantiopure R- and S-enantiomers of Betti base were obtained as the corresponding NO-ketal compound and salt with L-(+)-tartaric acid, respectively, in excellent yields with a practically foolproof operation.

  DOI：

  10.1021/jo051328j

文献信息

• Enantiopure 2,6-disubstituted piperidines bearing one alkene- or alkyne-containing substituent: preparation and application to total syntheses of indolizidine-alkaloids
  作者：Hui Liu、Deyong Su、Guolin Cheng、Jimin Xu、Xinyan Wang、Yuefei Hu

  DOI：10.1039/b927007h

  日期：——

  general and efficient procedure for the preparation of 2,6-disubstituted piperidines bearing one alkene- or alkyne-containing substituent was developed by using non-racemic Betti base as a chiral auxiliary. Many chiral benzylamines are excellent auxiliaries, but they were rarely used for this purpose because of the inefficient removal of the N-benzyl auxiliary residue under non-hydrogenative conditions

  通过使用非外消旋的Betti碱作为手性助剂，开发了一种制备带有一个含烯烃或炔烃取代基的2,6-二取代哌啶的通用有效方法。许多手性苄胺是极好的助剂，但由于在非氢化条件下不能有效去除N-苄基辅助残基，因此很少用于此目的。我们发现ñ，ñ-二取代的贝蒂碱衍生物具有典型的曼尼希结构 邻萘酚。当它进行碱催化的生成时邻醌甲基化物，实现了有效的非氢化N-脱苄基作用，并且烯烃和炔烃基团得以幸存。为了证明该方法的有效性和产品的多功能性，采用了不对称的总合成方法吲哚嗪-生物碱 （-）-167B， （-）-195小时， （-）-209D 和 （-）-223AB 完成了。
• Acid promoted CIDT for the deracemization of dihydrocinnamic aldehydes with Betti's base
  作者：Goffredo Rosini、Claudio Paolucci、Francesca Boschi、Emanuela Marotta、Paolo Righi、Francesco Tozzi

  DOI：10.1039/c0gc00013b

  日期：——

  Racemic α-epimerizable and unfunctionalized aldehydes have been converted into enantiomerically enriched mixtures through a sequence of (i) a conversion into the diastereoisomeric 3-substituted 1-phenyl-2,3-dihydro-1H-naphtho[1,2-e][1,3]oxazines by reaction with the (R)- or (S)-1-(α-aminobenzyl)-2-naphthol (Betti's base), (ii) an acid promoted crystallization-induced diastereoisomer transformation (CIDT), and (iii) a clean cleavage of the dihydro-1,3-naphthoxazinic ring of the enriched diastereoisomer, easily collected by filtration, allowing the recovery of the enantiomerically enriched aldehydes and the chiral auxiliary.

  对映体的α-可互变和未功能化的醛通过以下步骤转化为富含对映体的混合物：(i) 与(R)-或(S)-1-(α-氨基苄基)-2-萘酚（Betti碱）反应，转化为二面体异构体的3-取代1-苯基-2,3-二氢-1H-萘并[1,2-e][1,3]氧杂啉；(ii) 促酸的结晶诱导二面体异构体转化（CIDT）；(iii) 清洁地切割富集的二面体异构体的二氢-1,3-萘氧杂烯环，易于过滤收集，从而回收富含对映体的醛和手性辅助剂。
• Novel preparation of non-racemic 1-[α-(1-azacycloalkyl)benzyl]-2-naphthols from Betti base and their application as chiral ligands in the asymmetric addition of diethylzinc to aryl aldehydes
  作者：Jun Lu、Xuenong Xu、Shaozhong Wang、Cunde Wang、Yuefei Hu、Hongwen Hu

  DOI：10.1039/b204534f

  日期：——

  A novel route for the preparation of non-racemic 1-[α-(1-azacycloalkyl)benzyl]-2-naphthols was developed, which involves regioselective N-cycloalkylation of the Betti base with dials in the presence of NaBH3CN to give 1-azacycloalka[2,1-b]oxazine followed by the selective cleavage of a C–O bond with LiAlH4. As a new family of chiral ligands, their application in the enantioselective addition of diethylzinc to aryl aldehydes was tested. The ligands incorporating pyrrolidine and piperidine led to highly efficient asymmetric induction to give products in up to 96% yield and 99% ee.

  开发了一种制备非外消旋的1-[α-(1-氮杂环烷基)苯基]-2-萘醇的创新路线，该方法涉及在NaBH3CN的存在下对Betti碱进行区域选择性的N-环烷基化，与二醛反应生成1-氮杂环烷基[2,1-b]噁唑，随后用LiAlH4选择性断裂C–O键。作为一种新的手性配体家族，我们测试了其在二乙基锌对芳基醛进行对映选择性加成中的应用。结合呱啉和哌啶的配体实现了高效的非对称诱导，生成的产物收率高达96%，对映体过量（ee）达到99%。
• A New Approach to the Enantioseparation of Betti Bases
  作者：Vladimir Alfonsov、Kirill Metlushka、Charles McKenna、Boris Kashemirov、Olga Kataeva、Viktor Zheltukhin、Dilyara Sadkova、Alexey Dobrynin

  DOI：10.1055/s-2007-967941

  日期：2007.2

  An improved method for enantioseparation of racemic 1-(α-aminobenzyl)-2-naphthols has been developed by the reaction in situ of Betti base product mixtures with l-(+)-tartaric acid taken in a 1:1 ratio. The products of this reaction are (-)-1-(α-aminobenzyl)-2-naphthol tartrate, the acetal of benzaldehyde and tartaric acid as well as (+)-1,3-diaryl-2,3-dihydro-1H-naphth[1,2-e][1,3]oxazine, which can be easily separated by crystallization.

  通过将Betti碱产品混合物与l-(+)-酒石酸以1:1的比例进行原位反应，已开发出一种改进的对映体1-(α-氨基苄基)-2-萘酚的对映体分离方法。该反应的产物是(-)-1-(α-氨基苄基)-2-萘酚酒石酸盐、苯甲醛和酒石酸的缩醛以及(+)-1,3-二芳基-2,3-二氢-1H-萘并[1,2-e][1,3]恶嗪，可通过结晶法轻松分离。
• Enantioselective Molecular Recognition in a Flexible Self-Folding Cavitand
  作者：Rubén Álvarez-Yebra、Ricard López-Coll、Pere Galán-Masferrer、Agustí Lledó

  DOI：10.1021/acs.orglett.3c00463

  日期：2023.5.12

  We report a chiral deep cavitand receptor based on calix[5]arene stabilized by a cooperative network of hydrogen bonds and having a highly flexible structure. The cavitand displays enantioselective molecular recognition with a series of chiral quaternary ammonium salts, providing unprecedented stability ratios between the corresponding diastereomeric host–guest complexes. Molecular dynamics simulations

  我们报告了一种基于杯 [5] 芳烃的手性深腔受体，该受体通过氢键协同网络稳定并具有高度灵活的结构。cavitand 显示出对一系列手性季铵盐的对映选择性分子识别，在相应的非对映体主客体复合物之间提供前所未有的稳定性比。分子动力学模拟证实了新宿主的更高灵活性以及与间苯二酚 [4] 芳烃衍生的自折叠腔体有关的优异诱导拟合行为的出现。