Butyraldehyde (+)-(R)-1-amino-2-(methoxymethyl)pyrrolidinehydrazone | 319439-76-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: Butyraldehyde (+)-(R)-1-amino-2-(methoxymethyl)pyrrolidinehydrazone
• 英文别名: (E)-N-[(2R)-2-(methoxymethyl)pyrrolidin-1-yl]butan-1-imine
• CAS: 319439-76-4
• 化学式: C₁₀H₂₀N₂O
• 分子量: 184.282
• InChiKey: RHIHIEHYVBZATF-UEUZTHOGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  24.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Butyraldehyde (+)-(R)-1-amino-2-(methoxymethyl)pyrrolidinehydrazone 在 magnesium monoperoxyphthalate hexahydrate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 phosphate buffer 、 正己烷 为溶剂， 反应 1.0h， 生成 (R)-methyl-3-cyanopentanoate
  参考文献：
  名称：

  Asymmetric Synthesis of β-Substituted γ-Lactams Employing the SAMP-/RAMP-Hydrazone Methodology. Application to the Synthesis of (R)-(-)-Baclofen

  摘要：

  A short and efficient asymmetric synthesis of beta-substituted gamma-lactams is described. Key steps are the alpha-alkylation of aldehyde SAMP-hydrazones with alkyl bromoacetates, their MMPP mediated conversion to the corresponding nitriles and a reductive cyclization with Raney Ni or Ni boride to the title pyrrolidin-2-ones. The P-substituted gamma-lactams are obtained in three steps, good overall yields (27-78%) and excellent enantiomeric excesses (ee = 93-99%). The applicability of this procedure for the asymmetric synthesis of GABAs (gamma-aminobutyric acids) is demonstrated for (R)-(-)-baclofen hydrochloride, which is obtained in 4 steps, 55% yield and 94% ee.

  DOI：

  10.3987/com-05-s(k)41
• 作为产物：
  描述：

  1-氨基-2-（甲氧基甲基）-吡咯 、 正丁醛 以100%的产率得到Butyraldehyde (+)-(R)-1-amino-2-(methoxymethyl)pyrrolidinehydrazone
  参考文献：
  名称：

  Asymmetric Synthesis of β-Substituted γ-Lactams Employing the SAMP-/RAMP-Hydrazone Methodology. Application to the Synthesis of (R)-(-)-Baclofen

  摘要：

  A short and efficient asymmetric synthesis of beta-substituted gamma-lactams is described. Key steps are the alpha-alkylation of aldehyde SAMP-hydrazones with alkyl bromoacetates, their MMPP mediated conversion to the corresponding nitriles and a reductive cyclization with Raney Ni or Ni boride to the title pyrrolidin-2-ones. The P-substituted gamma-lactams are obtained in three steps, good overall yields (27-78%) and excellent enantiomeric excesses (ee = 93-99%). The applicability of this procedure for the asymmetric synthesis of GABAs (gamma-aminobutyric acids) is demonstrated for (R)-(-)-baclofen hydrochloride, which is obtained in 4 steps, 55% yield and 94% ee.

  DOI：

  10.3987/com-05-s(k)41

文献信息

• Asymmetric Total Synthesis of (−)-Callystatin A and (−)-20-epi-Callystatin A Employing Chemical and Biological Methods
  作者：Dieter Enders、Jose L. Vicario、Andreas Job、Michael Wolberg、Michael Müller

  DOI：10.1002/1521-3765(20020916)8:18<4272::aid-chem4272>3.0.co;2-k

  日期：2002.9.16

  second intermediate 4 the asymmetric alpha-alkylation of an O-protected derivative of 4-hydroxybutanal was performed exploiting the SAMP/RAMP hydrazone alkylation methodology, and followed by a highly Z-selective Horner-Wadsworth-Emmons reaction under modified conditions. For the synthesis of the polypropionate fragment 5 a diastereoselective syn-aldol reaction was employed between a chiral ethyl ketone

  有效的细胞毒性海洋天然产物（-）-Callystatin A及其20-epi类似物的有效不对称全合成已经实现。合成途径涉及三个片段的制备，以在途径的末端彼此偶联。使用3,5-二氧代羧酸酯的生物催化对映选择性还原作为关键步骤获得了第一片段3。对于第二中间体4，利用SAMP / RAMP alkyl烷基化方法进行了O保护的4-羟基丁醛衍生物的不对称α-烷基化反应，然后在修饰条件下进行了高度Z选择性的Horner-Wadsworth-Emmons反应。为了合成聚丙烯酸酯片段5，在手性乙基酮和α-取代的手性醛之间进行了非对映选择性的顺式羟醛反应，两者均通过其相应的RAMP的不对称烷基化再次制备成对映体纯形式。最后，这三个结构单元通过烯丙基三丁基phosph的高度E-选择性Wittig反应偶联，在最终氧化/脱保护序列后得到目标化合物。
• Asymmetric Total Synthesis of (−)-Pironetin Employing the SAMP/RAMP Hydrazone Methodology
  作者：Dieter Enders、Sylvie Dhulut、Daniel Steinbusch、Audrey Herrbach

  DOI：10.1002/chem.200601672

  日期：2007.5.7

  convergent asymmetric total synthesis of pironetin (1), a polyketide with immunosuppressive, antitumor, and plant-growth regulating activities is described. The synthesis was realized by coupling between the C(8)-C(14) 2 and C(7)-C(2) 15 fragments, respectively, by using a Mukaiyama-aldol reaction. The stereogenic centers of each fragment were generated by employing the SAMP/RAMP hydrazone (SAMP=(S)-1-

  描述了聚合的不对称全合成的吡咯丁酮（1），一种具有免疫抑制，抗肿瘤和植物生长调节活性的聚酮化合物。通过使用Mukaiyama-aldol反应分别在C（8）-C（14）2和C（7）-C（2）15片段之间偶联来实现合成。通过将SAMP / RAMP（SAMP =（S）-1-氨基-2-甲氧基甲基吡咯烷，RAMP =（R-1--1-氨基-2-甲氧基甲基吡咯烷））作为关键步骤来生成每个片段的立体异构中心。二乙基酮的不对称α-烷基化允许C（10）立体中心2的引入，而15的立体中心C（4）和C（5）是通过不对称的醛醇缩合反应安装的。最后，阿尔法的形成
• Reptilian Chemistry: Enantioselective Syntheses of Novel Components from a Crocodile Exocrine Secretion
  作者：Zhicai Yang、Athula B. Attygalle、Jerrold Meinwald

  DOI：10.1055/s-2000-8229

  日期：——

  Enantioselective syntheses of the two naturally-occurring diastereomers of dianeackerone (1a and 1b) and of a closely related steroidal β-oxo ester (2), characterized from the paracloacal glandular secretion of the African dwarf crocodile, Osteolaemus tetraspis, are described.

  描述了两种天然存在的 dianeackerone 的是否对映体异构体（1a 和 1b）以及一种与之密切相关的类固醇 β-氧酯（2）的对映选择性合成，这些化合物是从非洲侏儒鳄（Osteolaemus tetraspis）的旁肛腺分泌物中表征出的。
• Asymmetric Total Synthesis of (−)-Callystatin A Employing the SAMP/RAMP Hydrazone Alkylation Methodology
  作者：Jose L. Vicario、Andreas Job、Michael Wolberg、Michael Müller、Dieter Enders

  DOI：10.1021/ol0256116

  日期：2002.3.1

  [structure: see text] The asymmetric total synthesis of (-)-callystatin A has been achieved. The key steps generating the stereogenic centers rely on the asymmetric alpha-alkylation of aldehydes or ketones exploiting the SAMP/RAMP hydrazone alkylation methodology, as well as an enzymatic enantioselective reduction of a 3,5-dioxocarboxylate. For the construction of the alkene moieties, highly selective

  [结构：见正文]已实现（-）-卡利他汀A的不对称全合成。生成立体异构中心的关键步骤依赖于利用SAMP / RAMP alkyl烷基化方法以及3,5-二氧代羧酸酯酶促对映选择性还原的醛或酮的不对称α-烷基化。为了构建烯烃部分，采用了高度选择性的Wittig或Horner-Wadsworth-Emmons反应。
• Asymmetric Synthesis of β-Substituted γ-Lactams Employing the SAMP-/RAMP-Hydrazone Methodology. Application to the Synthesis of (R)-(-)-Baclofen
  作者：Dieter Enders、Oliver Niemeier

  DOI：10.3987/com-05-s(k)41

  日期：——

  A short and efficient asymmetric synthesis of beta-substituted gamma-lactams is described. Key steps are the alpha-alkylation of aldehyde SAMP-hydrazones with alkyl bromoacetates, their MMPP mediated conversion to the corresponding nitriles and a reductive cyclization with Raney Ni or Ni boride to the title pyrrolidin-2-ones. The P-substituted gamma-lactams are obtained in three steps, good overall yields (27-78%) and excellent enantiomeric excesses (ee = 93-99%). The applicability of this procedure for the asymmetric synthesis of GABAs (gamma-aminobutyric acids) is demonstrated for (R)-(-)-baclofen hydrochloride, which is obtained in 4 steps, 55% yield and 94% ee.