methyl (2R,1'S)-1-(1'-methyl)benzylazetidine-2-carboxylate | 204274-30-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl (2R,1'S)-1-(1'-methyl)benzylazetidine-2-carboxylate
• 英文别名: methyl 1-((S)-1'-phenylethyl)azetidine-2-carboxylate；methyl N-[(S)-phenylethyl]-azetidine-2(R)-carboxylic acid；methyl N-[(S)-methylbenzyl]azetidine-2-(R)-carboxylate；methyl (2R)-1-[(1S)-1-phenylethyl]azetidine-2-carboxylate
• CAS: 204274-30-6
• 化学式: C₁₃H₁₇NO₂
• 分子量: 219.283
• InChiKey: FMYIXIBSKQXTLX-CMPLNLGQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (2R,1'S)-1-(1'-methyl)benzylazetidine-2-carboxylate 在 吡啶 、 ammonium hydroxide 、 三氟乙酸酐 作用下， 以 1,4-二氧六环 为溶剂， 反应 3.0h， 生成 [1(1S),2R]-1-(1-phenyl-ethyl)-azetidine-2-carbonitrile
  参考文献：
  名称：

  通过 N-硼烷配合物的 α-烷基化，从手性 1-芳基乙胺合成光学活性 2-取代氮杂环丁烷-2-甲腈。

  摘要：

  研究了 N-((S)-1-芳基乙基)氮杂环丁烷-2-甲腈 3 通过形成 N-硼烷配合物 4 的碱促进 α-烷基化反应。例如，在-78℃下用1.2当量的LDA处理非对映体纯硼烷N-((S)-1'-(4''-甲氧基苯基)乙基)氮杂环丁烷-2-甲腈络合物(1S,2S,1'S)-4b ℃，然后在-78℃加入1.3当量的苄基溴并升温至室温，产生α-苄基化(2S,1'S)-5ba，产率72%，(2R,1'S)-5ba，产率2%。提出了这种非对映选择性α-烷基化的机制。我们的方法能够从市售的 (S)-(1-(4-甲氧基苯基)) 开始生产光学活性 2-取代氮杂环丁烷-2-甲腈，例如 α-苄基化 (S)-10a 和 (R)-10a乙）胺。

  DOI：

  10.1039/d1ra04585g
• 作为产物：
  描述：

  dimethyl (1'S)-(1'-methyl)benzylaminomalonate 在 2,6-二叔丁基-4-甲基苯酚 、 3 A molecular sieve 、 caesium carbonate 、 lithium chloride 作用下， 以 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 39.0h， 生成 methyl (2R,1'S)-1-(1'-methyl)benzylazetidine-2-carboxylate
  参考文献：
  名称：

  （S）-氮杂环丁烷-2-羧酸的有效途径。

  摘要：

  建立了一条新的有效途径，可分五个步骤制备（S）-氮杂环丁烷-2-羧酸（> 99.9％ee），并通过丙二酸酯中间体的总收率为48％。作为关键步骤，通过在1,2-二溴乙烷（1.5当量）和碳酸铯（2当量）中处理（S）-（1'-甲基）苄基氨基丙二酸二甲酯可实现有效的四元环形成（99％） DMF。（1'S）-1-（1'-甲基）苄基氮杂环丁烷-2,2-二羧酸二甲酯的Krapcho脱氧羰基化反应，是该环化过程的产物，优先形成所需（2S）（2.7：1，总收率78％） （1'S）-单酯，借助于在氮原子上引入的手性助剂。不需要的（2R，1'S）-异构体可以通过去质子化和随后的重质子化步骤以适当的立体化学转化为异构体。最后，

  DOI：

  10.1271/bbb.69.1892

文献信息

• Process for producing optically active azetidine-2-carboxylic acid
  申请人：Sumitomo Chemical Company, Limited

  公开号：US06114543A1

  公开（公告）日：2000-09-05

  The present invention provides a process for preparing optically active azetidine-2-carboxylic acids using readily available reagents of relatively low price in the industry. Thus, there is provided optically active azetidine-2-carboxylic acid, and a process for producing the same by subjecting optically active N-(alkylbenzyl)azetidine-2-carboxylic acid represented by the formula (1): ##STR1## to hydrogenolysis in the presence of a catalyst.

  本发明提供了一种使用工业上价格相对较低的易得试剂制备光学活性氮杂环丙氨酸的方法。因此，提供了光学活性氮杂环丙氨酸以及一种通过在催化剂存在下将式（1）表示的光学活性N-（烷基苯基）氮杂环丙氨酸进行氢解的方法。
• Enantioselective addition of alkynylzinc to arylaldehydes catalyzed by azetidino amino alcohols bearing an additional stereogenic center
  作者：Jun-Long Niu、Min-Can Wang、Liu-jie Lu、Guo-Liang Ding、Hui-Jie Lu、Qing-Tao Chen、Mao-Ping Song

  DOI：10.1016/j.tetasy.2009.10.031

  日期：2009.11

  Chiral azetidino amino alcohol ligands bearing an additional stereogenic center were readily prepared and used as catalysts for the asymmetric addition of alkynylzinc to aromatic aldehydes with enantioselectivities of up to 87% ee. The relationship between the reaction enantioselectivity and the structure of the chiral ligands was also evaluated in this reaction. The experimental results showed that the enantioselectivity level of the reaction was greatly influenced by the second stereogenic center attached to azetidine ring, but the stereochemical sense was only determined by the configuration of the azetidine ring. A possible transition structure for the catalytic asymmetric addition was also proposed. (C) 2009 Elsevier Ltd. All rights reserved.
• Azetidine based ligands in boron catalyzed asymmetric Diels-Alder reactions
  作者：Wim A.J. Starmans、Richard W.A. Walgers、Lambertus Thijs、René de Gelder、Jan M.M. Smits、Binne Zwanenburg

  DOI：10.1016/s0040-4020(98)00204-x

  日期：1998.5

  The preparation of a new class of azetidine-based auxiliaries and their selectivity in the BBr3 catalyzed Diets-Alder reaction is described. The results are compared with a similar proline-derived ligand and a known prolinol auxiliary. Results show that selectivities are highly dependent on the dienophile and the substituent of the chiral auxiliary. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Synthesis and X-ray analysis of 1-((1S)-phenylethyl)-azetidine-(2R)-piperidinamide
  作者：R. de Gelder、J. M. M. Smits、W. A. J. Starmans、L. Thijs、B. Zwanenburg

  DOI：10.1007/bf01668624

  日期：1996.9

  The crystal and molecular structure of a new azetidine-2-carboxylic amide derivative is described. The structure was solved by direct methods and refined by least squares methods to R1 = 0.0393 for 4264 reflections (with I > 2 sigma(I)). The structure consists of two independent molecules which are chemically the same with slight differences in geometry. Crystal data: C17H24N2O, monoclinic, space group P2(1), a = 8.3782(4), b = 20.0342(13), c = 9.7769(8)Angstrom, beta = 109.687(6)degrees, V = 1545.1(2)Angstrom(3), Z = 4.
• US6114543A
  申请人：——

  公开号：US6114543A

  公开（公告）日：2000-09-05