(S)-2-allyl-piperidine-1-carboxylic acid tert-butyl ester | 184535-09-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (S)-2-allyl-piperidine-1-carboxylic acid tert-butyl ester
• 英文别名: 2-allyl-piperidine-1-carboxylic acid tert-butyl ester；(S)-tert-butyl 2-allylpiperidine-1-carboxylate；tert-butyl (S)-2-allylpiperidine-1-carboxylate；tert-butyl 2-allylpiperidine-1-carboxylate；tert-butyl (2S)-2-prop-2-enylpiperidine-1-carboxylate
• CAS: 184535-09-9
• 化学式: C₁₃H₂₃NO₂
• 分子量: 225.331
• InChiKey: JABHSMGDKJBXQQ-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-2-allyl-piperidine-1-carboxylic acid tert-butyl ester 在 palladium dihydroxide 氢气 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 (R)-2-丙基哌啶
  参考文献：
  名称：

  Short enantioselective synthesis of sedridines, ethylnorlobelols and coniine via reagent-based differentiation

  摘要：

  The preparation of collections of structurally diverse small molecules is a useful tool for studying biology and medicine with chemistry. Herein, we demonstrate the versatility of the pure enantiomers of 2-(2-oxo-ethyl)-piperidine-1-carboxylic acid tertbutyl ester to prepare the biological active alkaloids sedridine, allosedridine, methylsedridine, methylallosedridine, ethylnorlobelol, and coniine in two steps and in a stereoselective way via a reagent-based differentiation. The described syntheses are a demonstration of the versatility of 2-(2-oxo-ethyl)-piperidine-1-carboxylic acid tert-butyl esters as chiral building blocks. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.05.032
• 作为产物：
  描述：

  (S)-N-((S)-2-Allyl-piperidin-1-yl)-2-hydroxy-N-methyl-2-phenyl-acetamide 在 lithium 、 potassium carbonate 作用下， 以 四氢呋喃 、 氨 、 水 为溶剂， 反应 1.0h， 生成 (S)-2-allyl-piperidine-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  通过手性全氢吡啶并[2,1-b] [1,3,4]-恶二嗪酮对哌啶进行对映选择性α-烷基化：合成两个甜氨酸对映体的简便方法

  摘要：

  据报道，使用任何一种扁桃酸作为手性助剂，涉及手性过氢吡啶并[2,1-b] [1,3,4]-恶二嗪酮的哌啶的对映选择性直接烷基化反应。（R）-以及（S）-甜氨酸的合成证明了该策略的应用。

  DOI：

  10.1016/s0040-4039(97)10438-5

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
• Preparation of Enantiopure Substituted Piperidines Containing 2-Alkene or 2-Alkyne Chains: Application to Total Syntheses of Natural Quinolizidine-Alkaloids
  作者：Guolin Cheng、Xinyan Wang、Deyong Su、Hui Liu、Fei Liu、Yuefei Hu

  DOI：10.1021/jo902615u

  日期：2010.3.19

  nonracemic Betti base as a chiral auxiliary. The key step is that the auxiliary residue was removed by a novel base-catalyzed N-debenzylation via a formation of o-quinone methide mechanism in stead of the traditional hydrogenolysis, by which the alkene or alkyne groups survived. By this method, ten 2-alkene- or 2-alkyne-containing chain substituted piperidines were prepared on the gram scale within

  通过使用非外消旋的Betti碱作为手性助剂，建立了制备对映体纯的含2个烯烃或2个炔烃的链取代哌啶的一般方法。关键步骤是代替传统的氢解反应，通过传统的氢解反应，通过邻甲基苯甲酸甲酯的形成，通过新颖的碱催化的N-脱苄基反应去除了辅助残基。通过这种方法，在数小时内以克为单位制备了十个含2-烯烃或2-炔烃的链取代的哌啶。为了证明该方法的有效性和产品的多功能性，使用（S）-2-烯丙基完成了天然生物碱（+）-peltierine，（-）-lasubine II和（+）-cermizine C的总合成--N -Boc-哌啶为通用成分。
• Dynamic resolution of N-Boc-2-lithiopiperidine
  作者：Iain Coldham、Sophie Raimbault、Praful T. Chovatia、Jignesh J. Patel、Daniele Leonori、Nadeem S. Sheikh、David T. E. Whittaker

  DOI：10.1039/b810988e

  日期：——

  Dynamic thermodynamic resolution of N-Boc-2-lithiopiperidine is possible using a chiral ligand; the two enantiomers of this organolithium can be resolved with selectivities of up to 85 : 15 from a selection of 26 chiral diamino-alkoxide ligands screened.

  使用手性配体可以动态热力学分离N-Boc-2-锂基哌啶；从筛选的26种手性二氨基醇酸配体中，该有机锂化合物的两个对映体可以以高达85:15的选择性进行分离。
• Highly Enantioselective Catalytic Dynamic Resolution of <i>N</i>-Boc-2-lithiopiperidine: Synthesis of (<i>R</i>)-(+)-<i>N-</i>Boc-Pipecolic Acid, (<i>S</i>)-(−)-Coniine, (<i>S</i>)-(+)-Pelletierine, (+)-β-Conhydrine, and (<i>S</i>)-(−)-Ropivacaine and Formal Synthesis of (−)-Lasubine II and (+)-Cermizine C
  作者：Timothy K. Beng、Robert E. Gawley

  DOI：10.1021/ja105772z

  日期：2010.9.8

  syntheses of both enantiomers of 2-substituted piperidines using a wide range of electrophiles. The CDR has been applied to the synthesis of (R)- and (S)-pipecolic acid derivatives, (+)-beta-conhydrine, (S)-(+)-pelletierine, and (S)-(-)-ropivacaine and the formal synthesis of (-)-lasubine II and (+)-cermizine C.

  在 TMEDA 存在下，使用手性配体 8 或其非对映异构体 9 的 rac-2-锂硫-N-Boc-哌啶催化动态拆分 (CDR) 导致使用广泛的 2-取代哌啶的两种对映体的高度对映选择性合成亲电试剂的范围。CDR 已应用于 (R)- 和 (S)-哌啶酸衍生物、(+)-β-conhydrine、(S)-(+)-pelletierine 和 (S)-(-)-ropivacaine 的合成(-)-lasubine II 和 (+)-cermizine C 的正式合成。
• A new asymmetric entry to 2-substituted piperidines. A concise synthesis of (+)-coniine, (−)-pelletierine, (+)-δ-coniceine, and (+)-epidihydropinidine
  作者：Hiroki Takahata、Minoru Kubota、Seiki Takahashi、Takefumi Momose

  DOI：10.1016/0957-4166(96)00395-3

  日期：1996.10

  A new asymmetric route to 2-substituted piperidines involving the Sharpless asymmetric dihydroxylation (AD) of 5-hexenylazide 1 and an intramolecular aminocyclization as crucial steps and its application to the asymmetric synthesis of four piperidine alkaloids, (+)-coniine 2, (−)-pelletierine 3, (+)-δ-coniceine 4, and (+)-epidihydropinidine 5 is presented.

  涉及5-己烯基叠氮化物1的Sharpless不对称二羟基化（AD）和分子内氨基环化作为关键步骤的2取代哌啶的新不对称路线及其在四个哌啶生物碱（+）-coniine 2的不对称合成中的应用，（-呈现了）-Peltierine 3，（+）-δ-可卡因4和（+）-epidihydropinidine 5。