α-Methoxy-α-(9-anthryl)acetic acid | 160798-26-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: α-Methoxy-α-(9-anthryl)acetic acid
• 英文别名: 2-Anthracen-9-yl-2-methoxyacetic acid；2-anthracen-9-yl-2-methoxyacetic acid
• CAS: 160798-26-5
• 化学式: C₁₇H₁₄O₃
• 分子量: 266.296
• InChiKey: NYBVEDXLZOESOE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  α-Methoxy-α-(9-anthryl)acetic acid 在 三氟乙酸 作用下， 以 正庚烷 、 异丙醇 为溶剂， 生成 (S)-9-anthrylmethoxyacetic acid 、 (-)-(R)-α-methoxy-α-(9-anthryl)acetic acid
  参考文献：
  名称：

  手性1,2-二元醇：通过NMR对其绝对构型的分配变得容易

  摘要：

  通过制备双（R）-和双（S）-9-AMA酯衍生物，然后比较NMR的NMR化学位移，可以轻松确定1,2-伯/仲二醇的绝对构型。非对位亚甲基质子中的两个衍生物。或者，如果分析了与CαH质子相对应的信号随温度的演变，则可以仅使用一种导数进行赋值。

  DOI：

  10.1021/ol9021639
• 作为产物：
  描述：

  (+/-)-ethyl α-hydroxy-α-(9-anthryl)acetate 在 silver(l) oxide 作用下， 生成 α-Methoxy-α-(9-anthryl)acetic acid
  参考文献：
  名称：

  Conformational Structure and Dynamics of Arylmethoxyacetates: DNMR Spectroscopy and Aromatic Shielding Effect

  摘要：

  The ground state conformational geometry and energy of esters of (R)- and (S)-arylmethoxyacetic acids were evaluated from low temperature H-1 and C-13 NMR spectra and by means of MM, AM1, and aromatic shielding effect calculations. In solution, the title compounds are constituted by two rotamers in equilibrium. Rotamer ap has the C-alpha-O and C=O bonds antiperiplanar and rotamer sp (lower in energy by 0.4-1.1 kcal/mol) has these bonds synperiplanar. In both the ap and the sp the aryl ring is ca. perpendicular to the C=O bond and coplanar with the CalphaH bond. Their relative populations and its temperature dependence evaluated by DNMR spectra are in agreement with the stereoselectivity reported for Diels-Alder reactions of dienyl-AMAA esters and support the ''perpendicular model'' proposed to account for that stereoselectivity. For conformations in which the aryl ring shields the alcohol moiety of the ester, calculated ring current shielding increments compare well with experimental shift values obtained from low-temperature NMR spectra and agree with the conformational model used in the Mislow-Dale-Mosher-Trost method for chiral recognition by NMR.

  DOI：

  10.1021/jo00108a008

文献信息

• [EN] PROCESSES FOR THE SYNTHESIS OF CHIRAL 1-ALKANOLS<br/>[FR] PROCÉDÉS DE SYNTHÈSE DE 1-ALCANOLS CHIRAUX
  申请人：PURDUE RESEARCH FOUNDATION

  公开号：WO2015106045A1

  公开（公告）日：2015-07-16

  The invention relates to highly enantioselective processes for the synthesis of chiral 1-alkanols via Zr-catalyzed asymmetric carboalumination of alkenes.

  这项发明涉及通过锆催化的不对称烯烃碳铝化反应合成手性1-烷醇的高对映选择性过程。
• PROCESSES FOR THE SYNTHESIS OF CHIRAL 1-ALKANOLS
  申请人：PURDUE RESEARCH FOUNDATION

  公开号：US20160332940A1

  公开（公告）日：2016-11-17

  The invention relates to highly enantioselective processes for the synthesis of chiral 1-alkanols via Zr-catalyzed asymmetric carboalumination of alkenes.

  这项发明涉及通过Zr催化的不对称烯烃碳硼烷化反应合成手性1-烷醇的高对映选择性过程。
• Myrioneurinol: a novel alkaloid skeleton from Myrioneuron nutans
  作者：Van Cuong Pham、Akino Jossang、Thierry Sévenet、Van Hung Nguyen、Bernard Bodo

  DOI：10.1016/j.tet.2007.08.095

  日期：2007.11

  A new alkaloid, myrioneurinol (1), was isolated from the leaves of Myrioneuron nutans and its structure determined from spectral analysis, including mass spectrometry and 2D NMR. Myrioneurinol (1) presented an unprecedented fused tetracyclic skeleton. The absolute configuration was established by the modified Mosher's method, using (R)- and (S)-9-anthrylmethoxyacetic acid (9-AMAA). A plausible biosynthetic

  一种新的生物碱，myrioneurinol（1），从叶片分离Myrioneuron碱草，其结构从波谱分析测定，包括质谱和二维核磁共振。Myrioneurinol（1）呈现了前所未有的融合四环骨架。通过改进的Mosher方法，使用（R）-和（S）-9-蒽甲氧基乙酸（9-AMAA）确定绝对构型。一种可能的生物合成途径从通过Δ-piperideine L-赖氨酸开始提出了1与nitraramine生物合成和相关生物碱比较。
• Aureobasidium pullulans as a key for the preparation of optical purity (R)-2-(anthracen-9-yl)-2-methoxyacetic acid – The chiral auxiliary reagent in determination of absolute configuration
  作者：Renata Kołodziejska、Marcin Wróblewski、Renata Studzińska、Aleksandra Karczmarska-Wódzka、Izabela Grela、Beata Augustyńska、Bożena Modzelewska-Banachiewicz

  DOI：10.1016/j.molcatb.2015.05.007

  日期：2015.11

  Optically pure (R)-2-(anthracen-9-yl)-2-methoxyacetic acid ((R)-9-AMA) was obtained. The most important stage of the synthesis generating chirality and ensuring high enantioselectivity was the stage of desymmetrization of prochiral α-ketoester. Enzymatic biotransformation was used in the presence of Saccharomyces cerevisiae and Aureobasidium pullulans. Biotransformation using S. cerevisiae leads to

  得到光学纯的（R）-2-（蒽-9-基）-2-甲氧基乙酸（（R）-9-AMA）。产生手性并确保高对映选择性的最重要的合成阶段是前手性α-酮酸酯的不对称化阶段。在酿酒酵母和金黄色葡萄球菌的存在下进行酶促生物转化。使用酿酒酵母进行生物转化会导致对映体过量65–70％（R-异构体）。的抗真菌剂保护博尼含有的活细胞A.霉允许获得对映体纯的（- [R）-9- AMA。
• Solvent-free Friedel-Crafts Reaction for Regioselective Synthesis of Ethyl (9-Anthryl)glyoxylate and Chiral Resolution of (±)-(9-Anthryl)hydroxyacetic Acid
  作者：Bao-Lin Li、Zhen-Guo Zhang、Wei Wang、Jin Li、Chou-Wen Wang

  DOI：10.1515/znb-2008-0111

  日期：2008.1.1

  A green chemistry-based highly regioselective synthesis of ethyl (9-anthryl)glyoxylate was achieved by solvent-free Friedel-Crafts reaction at r. t. Several derivatives of ethyl (9-anthryl)glyoxylate were also synthesized. Ethyl (9-anthryl)hydroxyacetate was obtained almost quantitatively by reduction of ethyl (9-anthryl)glyoxylate with NaBH₄, and (9-anthryl)methoxyacetic acid was prepared by methylation of ethyl (9-anthryl)hydroxyacetate with CH₃I in the presence of Ag₂O and hydrolysis of ethyl (9-anthryl)methoxyacetate. The hydrolysis of ethyl (9-anthryl)hydroxyacetate gave racemic (9-anthryl)hydroxyacetic acid, and the racemate was successfully resolved by crystallization of the diastereomeric salts resulting from the reaction of (±)-(9-anthryl)hydroxyacetic acid with (-)-ephedrine. As a byproduct, crystals containing racemic (±)-(9-anthryl)hydroxyacetate and protonated (-)-ephedrine were isolated and their structures determined by X-ray diffraction.

  通过无溶剂的费托合成反应在室温下实现了对乙酸乙酯(9-蒽基)甘酸酯的高度区域选择性绿色合成。还合成了几种乙酸乙酯(9-蒽基)甘酸酯的衍生物。通过NaBH₄还原乙酸乙酯(9-蒽基)甘酸酯可以几乎定量地得到乙酸乙酯(9-蒽基)羟基乙酸酯，通过在Ag₂O存在下甲基化乙酸乙酯(9-蒽基)羟基乙酸酯并水解可以得到(9-蒽基)甲氧基乙酸酸。对乙酸乙酯(9-蒽基)羟基乙酸酯的水解得到了外消旋的(9-蒽基)羟基乙酸，而该外消旋体成功通过(-)-麻黄碱的反应生成二对映异构体盐的结晶分离得到。作为副产物，还分离出含有外消旋的(±)-(9-蒽基)羟基乙酸酯和质子化的(-)-麻黄碱的晶体，并通过X射线衍射确定了它们的结构。