ethyl (S)-2-(trityloxy)propanoate | 123077-62-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: ethyl (S)-2-(trityloxy)propanoate
• 英文别名: ethyl (2S)-2-trityloxypropanoate
• CAS: 123077-62-3
• 化学式: C₂₄H₂₄O₃
• 分子量: 360.453
• InChiKey: CPQCYRMHGOMCPW-IBGZPJMESA-N

物化性质

• 沸点：
  469.9±40.0 °C(Predicted)
• 密度：
  1.107±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl (S)-2-(trityloxy)propanoate 在 正丁基锂 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 8.33h， 生成 tert-butyl (3S,4S)-3-(benzylamino)-4-trityloxypentanoate
  参考文献：
  名称：

  Highly Diastereoselective Conjugate Addition of Lithium Dialkylamides to α,β-Unsaturated Esters Having a Chiral Center at the γ-Position

  摘要：

  The conjugate addition of lithium amides 2 to tert-butyl 4-(OR)-substituted-2-pentenoates 1 produced a mixture of the syn-and anti-amino esters (3 and 4) in high yields. Sterically bulky OR groups, such as trityloxy and tert-butyldiphenylsilyloxy, gave the syn diastereomer 3 either exclusively or predominantly. The syn-selectivity may be explained by a modified Felkin-Anh model. The use of tert-butyldimethylsilyloxy as an OR group afforded a nearly 1:1 mixture of diastereoisomers, and the use of the smallest MeO group produced a 63:37 mixture of the syn 3 and anti isomer 4. The presence of Me group at the alpha-position (C-2 position) of the enoate enhanced the syn diastereoselectivity up to 100%; the conjugate addition to tert-butyl 4-methoxy-2-methyl-2-pentenoate (17) gave the syn-isomer 18 exclusively. This enhancement may be explained by the combination of chelation and allylic strain model 19 in which the smallest H orients inside to avoid an allylic strain. A phenyl group at the gamma-position enhanced the anti selectivity in the case of gamma-alkoxy-alpha,beta-enoates such as isopropyl 4-[(tert-butyldimethylsilyl)oxy]-4-phenyl-2-buteonoate (20), and in the case of gamma-alkyl-alpha,beta-enoates such as tert-butyl 4-phenyl-2-pentenoate (27).

  DOI：

  10.1021/jo970435d
• 作为产物：
  描述：

  L(-)-乳酸乙酯 、 三苯基氯甲烷 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以100%的产率得到ethyl (S)-2-(trityloxy)propanoate
  参考文献：
  名称：

  高立体选择性醚指导的钯催化氮杂-克莱森重排。

  摘要：

  使用相邻的醚基团来指导钯（II）催化剂的面部配位，已实现了高度立体选择性的烯丙基三氯乙亚氨酸酯重整为烯丙基三氯酰胺。

  DOI：

  10.1039/b501346c

文献信息

• Convenient method for the preparation of trityl ethers from secondary alcohols.
  作者：Sandrine Colin-Messager、Jean-Pierre Girard、Jean-Claude Rossi

  DOI：10.1016/s0040-4039(00)79058-7

  日期：1992.5

  The preparation of trityl ethers from secondary alcohols (10 mmol) with triphenylmethyl chloride (1.2 eq.) is carried out at room temperature by using DBU (1.4 eq.) as base in CH2Cl2. The high yielding procedure is very simple and its applicability is general.

  在室温下，通过使用DBU（1.4当量）作为碱在CH 2 Cl 2中，由仲醇（10 mmol）与三苯甲基氯（1.2当量）制备三苯甲基醚。高产量的程序非常简单，其适用性是普遍的。
• Trityl Ethers: Molecular Bevel Gears Reporting Chirality through Circular Dichroism Spectra
  作者：Jacek Ściebura、Paweł Skowronek、Jacek Gawronski

  DOI：10.1002/anie.200902167

  日期：2009.9.7

  More than a protecting group: The trityl group senses the chirality of an alkyl substituent in chiral trityl ethers. The CD spectra of trityl‐protected alcohols are highly sensitive to the chirality of the alcohol. The use of a trityl CD sensor provides new insight into the structure and mode of action of chiral molecular bevel gears and shows the relation between the absolute configurations of molecules

  不仅仅是保护基：三苯甲基可检测手性三苯甲基醚中烷基取代基的手性。三苯甲基保护的醇的CD光谱对醇的手性高度敏感。三苯甲基CD传感器的使用为手性分子锥齿轮的结构和作用方式提供了新的见解，并显示了分子的绝对构型与其棉花效应模式之间的关系。
• Benzyl Trityl Ether and DDQ as New Tritylating Reagents
  作者：Masato Oikawa、Hiroaki Yoshizaki、Shoichi Kusumoto

  DOI：10.1055/s-1998-1777

  日期：1998.7

  We describe herein a new tritylation procedure of alcohols using benzyl trityl ether and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. The reaction involves oxidative abstraction of one of the benzylic protons of benzyl trityl ether, followed by transformation of the generated benzyl trityl ether cation into a complex of benzaldehyde and trityl cation. The present procedure proceeds under mild neutral conditions to afford trityl ethers in generally good yields for primary alcohols, and in acceptable yields for several secondary alcohols.

  我们在此描述了一种使用苄基三苯基醚和2,3-二氯-5,6-二氰基-1,4-苯醌的醇类三苯基化的新程序。该反应涉及对苄基三苯基醚一个苄基质子的氧化抽提，随后生成的苄基三苯基醚阳离子转化为苯甲醛和三苯基阳离子的复合物。该程序在温和的中性条件下进行，通常能以良好的产率得到一醇的三苯基醚，对于几个二醇则能获得可接受的产率。
• Enantioselective total synthesis of macrosphelides A and E
  作者：Kavirayani R. Prasad、Phaneendra Gutala

  DOI：10.1016/j.tet.2011.04.099

  日期：2011.6

  Enantioselective synthesis of 16-membered trilactone macrolides, macrosphelide A and E from (S)-lactic acid is described. Key features of the synthesis include the utility of a hitherto unexplored β-ketophosphonate derived from lactic acid and Yamaguchi lactonization leading to the title compounds.

  描述了由（S）-乳酸对16元三内酯大环内酯，大环内酯A和E的对映选择性合成。合成的关键特征包括迄今未开发的衍生自乳酸的β-酮膦酸酯的使用和山口内酯化，生成标题化合物。
• Friedel–Crafts catalysts as assistants in the tritylation of less reactive hydroxyls
  作者：Roberta Bernini、Maurizio Maltese

  DOI：10.1016/j.tetlet.2010.05.144

  日期：2010.8

  Less reactive hydroxyls, such as those present in secondary alcohols and in some primary alcohols, phenols and carboxylic acids, were easily tritylated with the homogeneous assistance of equimolar quantities of chlorides of di- and trivalent metals in aprotic solvents. The metal ions allowed both high concentration of the effective reagent triphenylmethylcarbenium ion and mobilisation of the hydroxyl

  在质子惰性溶剂中，通过等摩尔量的二价和三价金属氯化物的均相助剂，反应性较低的羟基（例如存在于仲醇和某些伯醇，酚和羧酸中的羟基）很容易被三苯甲基化。金属离子允许高浓度的有效试剂三苯基甲基碳鎓离子和羟基质子的移动，从而引起快速的室温取代反应。实验条件温和，以至于其他保护基团，如烷基或三苯甲基保护的羧基和（9-芴基甲氧基羰基）-或三苯甲基保护的氨基均不受影响。