methyl 2-methoxy-2-(piperidin-1-yl)acetate | 13887-54-2

• 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 2-methoxy-2-(piperidin-1-yl)acetate
• 英文别名: Methyl I+/--methoxy-1-piperidineacetate；methyl 2-methoxy-2-piperidin-1-ylacetate
• CAS: 13887-54-2
• 化学式: C₉H₁₇NO₃
• 分子量: 187.239
• InChiKey: ZYGQPNCICNDGSW-UHFFFAOYSA-N

物化性质

• 沸点：
  71-72 °C(Press: 5 Torr)
• 密度：
  1.063±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-氟苯硼酸 、 methyl 2-methoxy-2-(piperidin-1-yl)acetate 在 2,2'-联吡啶 、 copper(I) bromide 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 1.0h， 以98%的产率得到methyl 2-(4-fluorophenyl)-2-(piperidin-1-yl)acetate
  参考文献：
  名称：

  Copper(I)-catalyzed coupling reaction of aryl boronic acids with N,O-acetals and N,N-aminals under atmosphere leading to α-aryl glycine derivatives and diarylmethylamine derivatives

  摘要：

  We demonstrated a copper(I)-catalyzed coupling reaction of aryl boronic acids with N,O-acetals and N,N-aminals leading to the synthesis of alpha-aryl glycines and diarylmethylamines. Under an ambient atmosphere, this catalytic system could be applied to the activation of a C(sp(3))-O bond of N,O-acetals with an ester and an aryl group, or without a coordinating substituent, as well as to a C(sp(3))-N bond of N,N-aminals. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.05.068
• 作为产物：
  描述：

  哌啶 、 甲氧基乙酸甲酯 在 N-溴代丁二酰亚胺(NBS) 、 三乙胺 作用下， 以 苯 、 四氢呋喃 为溶剂， 反应 3.0h， 以75%的产率得到methyl 2-methoxy-2-(piperidin-1-yl)acetate
  参考文献：
  名称：

  Copper(I)-catalyzed coupling reaction of aryl boronic acids with N,O-acetals and N,N-aminals under atmosphere leading to α-aryl glycine derivatives and diarylmethylamine derivatives

  摘要：

  We demonstrated a copper(I)-catalyzed coupling reaction of aryl boronic acids with N,O-acetals and N,N-aminals leading to the synthesis of alpha-aryl glycines and diarylmethylamines. Under an ambient atmosphere, this catalytic system could be applied to the activation of a C(sp(3))-O bond of N,O-acetals with an ester and an aryl group, or without a coordinating substituent, as well as to a C(sp(3))-N bond of N,N-aminals. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.05.068

文献信息

• Copper(II)-Catalyzed [4+1] Annulation of Propargylamines with<i>N</i>,<i>O</i>-Acetals: Entry to the Synthesis of Polysubstituted Pyrrole Derivatives
  作者：Norio Sakai、Hiroaki Hori、Yohei Ogiwara

  DOI：10.1002/ejoc.201500098

  日期：2015.3

  Described herein is the CuCl2-catalyzed [4+1] annulation of a variety of propargylamines with N,O-acetals that function as a C1 unit, leading to the production of polysubstituted pyrrole derivatives. Three important features of the N,O-acetal during the [4+1] annulation series via 5-endo-dig cyclization are described: an enolizable substituent adjacent to the central sp3-carbon is required, the central

  本文描述的是 CuCl 2 催化的各种炔丙胺与作为 C1 单元的 N,O-缩醛的 [4+1] 环化，导致产生多取代的吡咯衍生物。描述了 N,O-缩醛在通过 5-endo-dig 环化的 [4+1] 环化系列中的三个重要特征：需要与中心 sp3-碳相邻的可烯醇化取代基，中心 sp3-碳显示功能亲电试剂和亲核试剂的分离，仲胺的释放平稳地导致芳构化。
• Practical Synthesis of Natural Amino Acid Derivatives: Hf(OTf)₄-Catalyzed Mannich-Type Reaction of Ketene Silyl Acetals or Enol Silyl Ethers with <i>N</i>,<i>O</i>-Acetals as a Glycine Cation Equivalent
  作者：Norio Sakai、Asuka Sato、Takeo Konakahara

  DOI：10.1055/s-0029-1216743

  日期：——

  The authors demonstrated the Hf(OTf) 4 -catalyzed Mannich-type reaction of an enol silyl ether and a ketene silyl acetal with an N,O-acetat leading to the preparation of amino acid derivatives. In particular, use of the N,O-acetal having a bis(trimethylsilyl)amino group directly produced N-unprotected aspartic acid derivatives after a standard aqueous workup.

  作者展示了 Hf(OTf) 4 催化的烯醇甲硅烷基醚和烯酮甲硅烷基缩醛与 N,O-乙酸酯的曼尼希型反应，导致制备氨基酸衍生物。特别是，使用具有双（三甲基甲硅烷基）氨基的 N,O-缩醛在标准水处理后直接产生了 N-未保护的天冬氨酸衍生物。
• A practical approach to non-natural or N-unsubstituted α-arylglycine derivatives: Hf(OTf)4-doped Me3SiCl system-catalyzed aminomethylation of electron-rich arenes with a new type of N,O-acetal
  作者：Norio Sakai、Junichi Asano、Yuta Shimano、Takeo Konakahara

  DOI：10.1016/j.tet.2008.07.052

  日期：2008.9

  demonstrated the Hf(OTf)4-doped Me3SiCl system-catalyzed aminomethylation of electron-rich aromatic compounds, such as indoles and anilines, with new types of N,O-acetals having a variety of functional groups, such as cyano, ester, bis(trimethylsilyl)amino, diallylamino, and cyclic amino moieties, for the preparation of non-natural aromatic amino acid derivatives. Aminomethylation using an N,O-acetal with a

  作者已经证明了Hf（OTf）4掺杂的Me 3 SiCl系统催化的富电子芳族化合物（如吲哚和苯胺）的氨甲基化，以及具有各种官能团的新型N，O-乙缩醛，如氰基，酯，双（三甲基甲硅烷基）氨基，二烯丙基氨基和环状氨基部分，用于制备非天然芳香族氨基酸衍生物。在直接制备N-未取代的α-吲哚基甘氨酸衍生物的过程中，使用N，O-乙缩醛与双（三甲基甲硅烷基）氨基的氨基甲基化特别成功，该过程仅需进行标准的水性处理即可。
• The generation of iminium ions using chlorosilanes and their reactions with electron rich aromatic heterocycles
  作者：Harry Heaney、George Papageorgiou、Robert F. Wilkins

  DOI：10.1016/s0040-4020(96)01174-x

  日期：1997.2

  have been used to generate iminium ions from aminals and aminol ethers derived from secondary alkylamines, including glycine derivatives, in aprotic media which were shown to undergo reactions with electron rich aromatic heterocycles, including furan, to give mono-aminoalkylation products in good yields. Whereas chlorotrimethylsilane has been shown to generate iminium ions from aminol ethers, no evidence

  二氯二甲基硅烷和三氯甲基硅烷已被用于在质子惰性介质中从衍生自仲烷基胺（包括甘氨酸衍生物）的缩醛和氨基醚生成亚胺离子，该非质子介质已显示与富电子芳族杂环（包括呋喃）发生反应，从而得到良好的单氨基烷基化产物产量。氯三甲基硅烷已被证明可以从氨基醚中产生亚胺离子，但没有证据表明亚胺类化合物参与了亚胺离子的产生。的2,5-二取代Ñ -methylpyrrole在反应中的主要结果Ñ-甲基吡咯与缩醛在氯三甲基硅烷的存在下发生，其中没有氯化氢的积累发生，并且氯三甲基硅烷可以催化作用。实验结果，包括使用双（三甲基甲硅烷基）乙酰胺作为质子清除剂，以及一些相对速率数据，可以评估可能的机理。
• Facile Approach to Natural or Non-Natural Amino Acid Derivatives: Me₃SiCl-Promoted Coupling Reaction of Organozinc Compounds with N,O-Acetals
  作者：Norio Sakai、Junichi Asano、Yuki Kawada、Takeo Konakahara

  DOI：10.1002/ejoc.200801107

  日期：2009.2

  We have developed a Me3SiCl-promoted coupling reaction of aryl- and alkylzinc compounds, in-situ generated either by transmetalation of the corresponding organometallic reagents or by insertion of zinc metal into organic halides, with several N,O-acetals, which leads to the preparation of a variety of natural and non-natural amino acid derivatives. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim

  我们开发了一种 Me3SiCl 促进的芳基和烷基锌化合物的偶联反应，通过相应的有机金属试剂的金属转移或通过将锌金属插入有机卤化物中而原位生成，与几种 N，O-缩醛，这导致制备多种天然和非天然氨基酸衍生物。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)