methyl 1-[(1,1-dimethylethoxy)carbonyl]-2-piperidinepropanoate | 179685-64-4

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: methyl 1-[(1,1-dimethylethoxy)carbonyl]-2-piperidinepropanoate
• 英文别名: tert-butyl 2-(3-methoxy-3-oxopropyl)piperidine-1-carboxylate；2-(2-Methoxycarbonyl-ethyl)-piperidine-1-carboxylic acid tert-butyl ester
• CAS: 179685-64-4
• 化学式: C₁₄H₂₅NO₄
• 分子量: 271.357
• InChiKey: KZOREEKXGWTFQD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 1-[(1,1-dimethylethoxy)carbonyl]-2-piperidinepropanoate 在 劳森试剂 、 盐酸 、 氨 作用下， 以 甲醇 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Evaluation of pyrrolidin-2-imines and 1,3-thiazolidin-2-imines as inhibitors of nitric oxide synthase

  摘要：

  Syntheses and evaluation of pyrrolidin-2-imines and 1,3-thiazolidin-2-imines as inhibitors of nitric oxide synthase (NOS) are discussed. An extensive SAR was established for pyrrolidin-2-imines class of compounds. The amidines came out as the most potent inhibitors in addition to displaying selectivity. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2004.06.033
• 作为产物：
  描述：

  N-Boc-L-哌啶-2-羧酸 在 N-甲基吗啉 、 sodium tetrahydroborate 、 三乙基硼 、 三(三甲基硅基)硅烷 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 1.75h， 生成 methyl 1-[(1,1-dimethylethoxy)carbonyl]-2-piperidinepropanoate
  参考文献：
  名称：

  α-氨基酰基碲化物的脱羰基自由基偶联：γ-氨基和α，β-二氨基酸的一步制备以及加巴喷丁和甘露糖苷A的快速合成

  摘要：

  已开发出一种新的基于自由基的偶联方法，可从α-氨酰基碲化物单步生成各种γ-氨基酸和α，β-二氨基酸。在室温下被Et 3 B和O 2活化后，α-氨基酰基碲化物很容易通过容易的脱羰作用转化为α-氨基碳原子团，然后与丙烯酸酯或乙醛氧基肟醚发生分子间反应。这种温和而有效的方法有效地整合到了加巴喷丁和天然产物（-）-甘露酸A的快速合成途径中。

  DOI：

  10.1002/anie.201410186

文献信息

• Regioselective and Stereoselective Copper(I)-Promoted Allylation and Conjugate Addition of <i>N</i>-Boc-2-lithiopyrrolidine and <i>N</i>-Boc-2-lithiopiperidine
  作者：Iain Coldham、Daniele Leonori

  DOI：10.1021/jo100415x

  日期：2010.6.18

  regioselectively (SN2 mechanism). Addition to an enone or α,β-unsaturated ester occurs by 1,4-addition. Asymmetric deprotonation of N-Boc-pyrrolidine or dynamic resolution in the presence of a chiral ligand of N-Boc-2-lithiopiperidine followed by the zinc/copper chemistry was successful and gave the allylated pyrrolidine and piperidine products with good enantioselectivity, although use of the copper iodide

  铜盐已被筛选的转移金属化和电淬火ñ -叔丁氧羰基-2- lithiopyrrolidine（Ñ -Boc-2- lithiopyrrolidine）和Ñ -Boc-2- lithiopiperidine，通过去质子化而形成Ñ -Boc -吡咯烷和ñ - Boc-哌啶分别。然后，用氯化锌（溶解了氯化锂）进行重金属化，然后进行烯丙基化，生成区域异构体的混合物（S N 2和S N 2'产物），而用碘化铜·TMEDA进行重金属化，则区域选择性地进行烯丙基化（S N2机制）。通过1，4-加成发生烯键或α，β-不饱和酯的加成。N -Boc-吡咯烷的不对称去质子化或在N -Boc-2-lithiopiperidine的手性配体存在下的动态拆分以及随后的锌/铜化学反应是成功的，尽管使用了N -Boc-2-lithiopiperidine的手性配体，但烯丙基化的吡咯烷和哌啶产物具有良好的对映选择性碘化铜的化
• Dual Benzophenone/Copper‐Photocatalyzed Giese‐Type Alkylation of C(sp ³ )−H Bonds
  作者：Baptiste Abadie、Damien Jardel、Gianluca Pozzi、Patrick Toullec、Jean‐Marc Vincent

  DOI：10.1002/chem.201904111

  日期：2019.12.13

  benzophenone (BP) with a catalytic amount of Cu(OAc)2 . Under mild and operationally simple conditions, the Giese adducts resulting from the C(sp3 )-H functionalization of amines, alcohols, ethers, and cycloalkanes could be synthesized. Preliminary mechanistic studies have revealed that the reaction does not proceed through a radical chain, but through a dual BP/Cu photocatalytic process, in which both CuII

  C(sp3 )-H 键的光催化 Giese 型烷基化在 CC 键形成的原子经济背景下是非常有吸引力的反应。这种反应的主要限制是，当使用高度可聚合的烯烃受体，如未取代的丙烯酸酯、丙烯腈或甲基乙烯基酮时，自由基聚合通常成为主要或排他的反应途径。在此，我们报告说，当将二苯甲酮 (BP) 的光催化活性与催化量的 Cu(OAc)2 结合时，此类烯烃的聚合受到强烈限制或抑制。在温和且操作简单的条件下，可以合成由胺、醇、醚和环烷烃的 C(sp3 )-H 官能化产生的 Giese 加合物。
• α-(<i>N</i>-Carbamoyl)alkylcuprate Chemistry in the Synthesis of Nitrogen Heterocycles
  作者：R. Karl Dieter、Kai Lu

  DOI：10.1021/jo016053w

  日期：2002.2.1

  beta-ynoates, alpha-allenyl esters, or alpha.beta-enoates or enimides undergo N-Boc deprotection and cyclization onto the ester functionality upon treatment with PhOH/TMSCl, catecholboron bromide, or trimethylsilyl triflate. This two-pot sequence provides synthetic routes to 4-alkylidinepyrrolidine-2-ones, 4-alkylidinepyrrolizidin-2-ones, and 4-alkylidineindolizidin-2-ones via allenyl esters; pyrrolin-2-ones

  通过将α-（N-氨基甲酰基）烷基铜酸酯与α，β-壬酸酯，α-烯丙基酯或α-β-烯酸酯或亚胺偶联而获得的共轭加合物经过PhOH处理后进行N-Boc脱保护并环化成酯官能团/ TMSCl，溴化儿茶酚硼或三氟甲磺酸三甲基硅烷基酯。该两锅序列通过烯基酯提供了合成途径，以合成4-烷基吡啶并吡咯烷-2-酮，4-烷基吡啶并吡咯并丁-2-酮和4-烷基吡啶并吲哚并丁-2-酮。吡咯烷-2-酮，四氢吡咯嗪-2-酮和四氢吲哚嗪-2-酮通过α/β-羟酸酯形成; 通过α，β-烯酸酯或α.β-亚胺形成吡咯烷-2-酮，吡咯烷-2-酮和吲哚嗪-2-酮。γ-氨基甲酰基-α-β-烯酸酯不愿意进行E / Z异构化需要使用（Z）-β-碘-α，通过将HI加到炔基酯中可以容易地制备β-烯酸酯，以有效地制备吡咯烷酮，四氢吡咯烷酮和四氢吲哚酮。利用ω-官能化的α，η-酸酯或β-碘-α，β-烯酸酯可环化到ω-官能度上，从而提供了合成喹喔啉的途径。
• Conjugate Addition Reactions of α-Aminoalkylcuprates with α,β-Alkenyl-, α,β-Alkynyl-, α,β−β,γ-Allenyl-, and α,β−γ,δ-Dienyl Carboxylic Acid Derivatives, Nitriles, and Sulfoxides
  作者：R. Karl Dieter、Kai Lu、Sadanandan E. Velu

  DOI：10.1021/jo0056038

  日期：2000.12.1

  participate in 1,4-addition reactions with alpha, beta-unsaturated esters, thiol esters, imides, and nitriles in poor to excellent yields depending upon the electron-withdrawing substituent and the substitution pattern of the unsaturated substrate. These reagents also undergo conjugate addition reactions with alpha,beta-alkynyl esters, sulfoxides, and nitriles and with alpha,beta-beta,gamma-unsaturated allenyl

  由α-硫代氨基甲酸酯和CuCN.2LiCl制备的α-氨基烷基铜酸酯参与与α，β-不饱和酯，硫醇酯，酰亚胺和腈的1,4-加成反应，取决于吸电子取代基和不饱和底物的取代模式。这些试剂还与α，β-炔基酯，亚砜和腈以及α，β-β，γ-不饱和烯基酯进行共轭加成反应。在α-氨基烷基铜酸酯与烯丙基酯的共轭加成中实现了优异的立体控制，而立体选择性差导致向炔基衍生物的共轭加成。炔基加合物的脱保护和环化反应可得到吡咯烷-2-酮，
• Synthesis of 6- and 7-Membered Cyclic Enaminones: Scope and Mechanism
  作者：Micah J. Niphakis、Brandon J. Turunen、Gunda I. Georg

  DOI：10.1021/jo100907u

  日期：2010.10.15

  Six- and seven-membered cyclic enaminones can be prepared using common. environmentally benign reagents. Ammo acids are used as synthetic precursors allowing diversification and the incorporation of chirality The key reaction in this multistep process involves deprotection Boc-amino ynones and subsequent treatment with methanolic K2CO3 to induce cyclization. A beta-amino elimination side reaction was identified in a few labile substrates that led to loss of stereochemical purity of degradation. This process can be mitigated in specific cases using mild deprotection conditions NMR and deuteitum-labeling experiments provided valuable insight into the work kings and limitations of this reaction Although disguised as a 6-endo-dig cyclization, the reagents employed in the transformation play a direct role in bond-making and bond-breaking. thus changing die mode of addition to a 6-endo-trig cyclization This method can be used to construct an array of monocyclic and bicyclic scaffolds. many of which me found in well-known natural products (e g indolizidine, quinolizidine, and Stemona alkaloids).