(2R,5S)-5-Allyl-2,5-dihydro-3,6-dimethoxy-2-isopropylpyrazine | 143730-35-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 甲亚胺酸及其衍生物
• 英文名称: (2R,5S)-5-Allyl-2,5-dihydro-3,6-dimethoxy-2-isopropylpyrazine
• 英文别名: (2R,5S)-5-allyl-2,5-dihydro-2-isopropyl-3,6-dimethoxypyrazine；(2S,5R)-2-allyl-2,5-dihydro-5-isopropyl-3,6-dimethoxypyrazine；(2R,5S)-3,6-dimethoxy-2-propan-2-yl-5-prop-2-enyl-2,5-dihydropyrazine
• CAS: 143730-35-2
• 化学式: C₁₂H₂₀N₂O₂
• 分子量: 224.303
• InChiKey: HAHQBQXWZSNMSA-VHSXEESVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  43.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R,5S)-5-Allyl-2,5-dihydro-3,6-dimethoxy-2-isopropylpyrazine 在 盐酸 、 氨 、 methyloxirane 作用下， 反应 14.25h， 生成 (S)-(-)-2-氨基-4-戊烯酸
  参考文献：
  名称：

  Stereospecific synthesis of α-deuteriated α-amino acids: regiospecific deuteriation of chiral 3-isopropyl-2,5-dimethoxy-3,6-dihydropyrazines

  摘要：

  Base-catalysed deuteriation of (3R)- or (3S)-3-isopropyl-2.5-dimethoxy-3,6-dihydropyrazines in refluxing (CH3OH)-H-2-(H2O)-H-2 gives the [6-H-2(2)]-isotopomer in excellent yields without disturbing the stereogenic centre at C-3. These compounds provide convenient and efficient access to a range of (R)- and (S)-alpha-deuteriated alpha-amino acids, including serine, aspartic acid, allylglycine and phenylalanine, via alkylation of the butyllithium generated C-6 anion.

  DOI：

  10.1039/p19950000157
• 作为产物：
  描述：

  N-苄氧羰基-D-缬氨酸 在 palladium on activated charcoal N-甲基吗啉 、 正丁基锂 、 氢气 、 氯甲酸异丁酯 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 108.0h， 生成 (2R,5S)-5-Allyl-2,5-dihydro-3,6-dimethoxy-2-isopropylpyrazine
  参考文献：
  名称：

  Stereospecific synthesis of α-deuteriated α-amino acids: regiospecific deuteriation of chiral 3-isopropyl-2,5-dimethoxy-3,6-dihydropyrazines

  摘要：

  Base-catalysed deuteriation of (3R)- or (3S)-3-isopropyl-2.5-dimethoxy-3,6-dihydropyrazines in refluxing (CH3OH)-H-2-(H2O)-H-2 gives the [6-H-2(2)]-isotopomer in excellent yields without disturbing the stereogenic centre at C-3. These compounds provide convenient and efficient access to a range of (R)- and (S)-alpha-deuteriated alpha-amino acids, including serine, aspartic acid, allylglycine and phenylalanine, via alkylation of the butyllithium generated C-6 anion.

  DOI：

  10.1039/p19950000157

文献信息

• Ru(II)-Catalysis in preparation of sterically congested and stereochemically homogeneous heterospiranes
  作者：Jon Efskind、Christian Rømming、Kjell Undheim

  DOI：10.1039/a901913h

  日期：——

  Sterically highly crowded dienes may undergo RCM reactions to furnish heterocyclic bispiranes in high yields. The diene substrates were C1-bridged bis[(2R)-5-alkenyl-2,5-dihydro-3,6-dimethoxy-2-isopropylpyrazines]. The carbonyl or hydroxymethyl bridges were prepared in stereoselective reactions. A free hydroxy group in the present series was incompatible with the RCM reaction. The ring closure proceeded readily after O-methylation. The course of the stereochemical transformations has been verified by X-ray analyses.

  立体高度拥挤的二烯可通过 RCM 反应以高产率生成杂环双螺环。二烯底物是 C1 桥双[(2R)-5-烯基-2,5-二氢-3,6-二甲氧基-2-异丙基吡嗪]。羰基或羟甲基桥是通过立体选择性反应制备的。本系列中的游离羟基与 RCM 反应不相容。在 O-甲基化之后，闭环反应很容易进行。立体化学转化的过程已通过 X 射线分析得到验证。
• Homocoupling in the Preparation of Dimeric Cyclic Peptide Derivatives
  作者：Jon Efskind、Håkon Hope、Kjell Undheim

  DOI：10.1002/1099-0690(20022)2002:3<464::aid-ejoc464>3.0.co;2-j

  日期：2002.2

  A method for the preparation of dimeric (2R)-2,5-dihydro-2-isopropyl-3,6-dimethoxypyrazine and 5-alkenyl derivatives by homocoupling is described. Moderate stereoselectivity was observed. The major product has C2-symmetry. The course of the stereochemical transformations has been ascertained by a single crystal X-ray analysis. A C2-symmetrical bisallyl substrate in a RuII-catalyzed ring-closing metathesis

  一种制备二聚（2的方法- [R进行说明通过自偶联）-2,5-二氢-2-异丙基-3,6- dimethoxypyrazine和5 -链烯基衍生物。观察到中等的立体选择性。主要产物具有C 2对称性。立体化学转变的过程已经通过单晶X射线分析确定。在Ru II催化的闭环复分解反应中的C 2对称双烯丙基底物以> 95％的产率提供了相应的1,2-双（螺环化环二肽基）环己烷。
• Cycloisomerisations in Pd-Catalysed Spiroannulations onto Chiral Pyrazine Derivatives
  作者：Bjørg Møller、Kjell Undheim

  DOI：10.1002/ejoc.200390038

  日期：2003.1

  in cyclisation reactions of dienes with the chiral auxiliary (2R)-2,5-dihydro-2-isopropyl-3,6-dimethoxypyrazine. Extensive NMR assignments are described and used in structure determinations. Isomer identification has been verified by a separate unequivocal synthesis. Nickel catalysis with MeMgBr was compatible with cross-coupling in the spiroannulated chiral auxiliary. (© Wiley-VCH Verlag GmbH & Co.

  描述了一种用于 5-exo-trig-spiroannulations 的方法，该方法使用 Pd 配合物反式-双（μ-乙酰基）双 [o-（二-邻甲苯基膦酰基）苄基]二钯（II）作为催化剂在二烯与手性助剂 (2R)-2,5-二氢-2-异丙基-3,6-二甲氧基吡嗪。广泛的 NMR 分配被描述并用于结构测定。异构体鉴定已通过单独的明确合成验证。镍与 MeMgBr 的催化作用与螺环手性助剂中的交叉偶联相容。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Stereoselective synthesis of functionalised cycloalkene α-quaternary α-amino acid derivatives
  作者：Mioara Andrei、Kjell Undheim

  DOI：10.1016/j.tetasy.2003.10.013

  日期：2004.1

  A route for the preparation of unsaturated cyclic α-quaternary α-amino acid derivatives is described. Stepwise and stereocontrolled alkylations of the chiron (R)-2-isopropyl-3,6-dimethoxy-2,5-dihydropyrazine provided gem-disubstituted derivatives with an alkene and an alkoxo substituent. The Wacker oxidation was compatible for chemoselective oxidation of the alkene function. Formation of a methyl ketone

  描述了制备不饱和环状α-季α-氨基酸衍生物的途径。Chiron（R）-2-异丙基-3,6-二甲氧基-2,5-二氢吡嗪的逐步和立体控制的烷基化提供了具有烯烃和烷氧基取代基的宝石-二取代的衍生物。Wacker氧化兼容于烯烃官能团的化学选择性氧化。甲基酮或醛的形成取决于底物。二氧羰基基质中的螺环化反应是通过碳酸铯在乙腈中的分子内羟醛缩合实现的。区域化学是底物依赖性的。在温和的酸性条件下裂解杂螺烷提供环状α-季α-氨基酸衍生物。
• Ru(II)-catalyzed ring closing metathesis in stereoselective syntheses of constrained homoserine analogues
  作者：Kristin Hammer、Christian Rømming、Kjell Undheim

  DOI：10.1016/s0040-4020(98)00626-7

  日期：1998.9

  Stereoselective syntheses of cyclic alpha-amipo-gamma-hydroxycyclohexene- and cycloheptene-alpha-carboxylic acids are described. RCM cyclization reactions were effected by Ru(II)-catalysis on sterically homogenous hydroxylated dienes. The diene substrates were available by stepwise, stereoselective alkylations of (R)-2,5-dihydro-3,6-dimethoxy-2-isopropylpyrazine with bromoalkenes, ethylene oxide and subsequent transformations. (C) 1998 Elsevier Science Ltd. All rights reserved.