<2S,1R>-methyl <2-<(2-methoxyethoxy)methyl>-1-pyrrolidyl>(1-methyl-3-phenylpropyl)carbamate | 127222-03-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: <2S,1R>-methyl <2-<(2-methoxyethoxy)methyl>-1-pyrrolidyl>(1-methyl-3-phenylpropyl)carbamate
• 英文别名: (2S,1'R)-2-(2-methoxyethoxymethyl)-1-[N-(1-methyl-3-phenylpropyl)-N-methoxycarbonylamino]pyrrolidine；methyl N-[(2S)-2-(2-methoxyethoxymethyl)pyrrolidin-1-yl]-N-[(2R)-4-phenylbutan-2-yl]carbamate
• CAS: 127222-03-1
• 化学式: C₂₀H₃₂N₂O₄
• 分子量: 364.485
• InChiKey: FWFNSATVVFAGQB-MJGOQNOKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  26
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  51.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  <2S,1R>-methyl <2-<(2-methoxyethoxy)methyl>-1-pyrrolidyl>(1-methyl-3-phenylpropyl)carbamate 在 碘代三甲硅烷 、 氨 、 lithium 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 2.33h， 生成 (R)-N-(3,5-dinitrobenzoyl)-2-amino-4-phenylbutane
  参考文献：
  名称：

  Lithium/ammonia cleavage of the nitrogen-nitrogen bond in N-(methoxycarbonyl)- and N-acetylhydrazines

  摘要：

  DOI：

  10.1021/jo00312a034
• 作为产物：
  描述：

  (E)-N-[(2S)-2-(2-methoxyethoxymethyl)pyrrolidin-1-yl]-3-phenylpropan-1-imine 在 cerium(III) chloride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 17.5h， 生成 <2S,1R>-methyl <2-<(2-methoxyethoxy)methyl>-1-pyrrolidyl>(1-methyl-3-phenylpropyl)carbamate
  参考文献：
  名称：

  Organocerium additions to hydrazones: effects of reagent stoichiometry on efficiency and selectivity

  摘要：

  The effects of reagent stoichiometry on the efficiency and selectivity of organocerium additions to chiral and achiral hydrazones have been investigated. rhe reagent formed in-situ from 1 equiv of CH3Li and 0.33 equiv of CeCl3 adds efficiently (>65% yield) to N,N-dimethylhydrazone 1, but this same reagent reacts only sluggishly with chiral SAMEMP hydrazone 2 (<30% yield). The optimal stoichiometry of the organocerium reagent is 1:1 CH3Li/CeCl3, despite the fact that not all of the CeCl3 ig consumed in the transmetalation. At least 2 equiv of methyl nucleophile is required to obtain acceptable yields in additions to 2, suggesting that the auxiliary side chain inhibits the reactivity of the first equivalent of organometallic reagent and that binding of the reagent to one of the hydrazone nitrogen atoms facilitates addition. This hypothesis is supported by the observation that competitive ligands such as amines or alkoxides effectively inhibit the addition of organocerium reagents to 1. The active reagent formed at all mixing stoichiometries is proposed to be a trimethyllanthanide species on the basis of reactivity and the presence of ur reacted MCl3 at less than 3:1 CH3Li/MCl3 mixing ratios.

  DOI：

  10.1021/jo00055a008

文献信息

• Organocerium additions to proline-derived hydrazones: synthesis of enantiomerically enriched amines
  作者：Scott E. Denmark、James P. Edwards、Theodor Weber、David W. Piotrowski

  DOI：10.1016/j.tetasy.2010.04.042

  日期：2010.5

  The addition of organocerium reagents (from both organolithium and organomagnesium precursors) to chiral aldehyde hydrazones prepared from 1-aminoproline derivatives has been studied. The additions proceed in good yield and high diastereoselectivity and with good nucleophile (Me, n-Bu, i-Pr, t-Bu, Ph, etc.) and substrate scope (alkyl, alkenyl and aryl). The resulting hydrazines can be converted to

  已经研究了将有机铈试剂（来自有机锂和有机镁前体）添加到由1-氨基脯氨酸衍生物制备的手性醛中。添加以高收率和高非对映选择性以及良好的亲核试剂（Me，n- Bu，i- Pr，t- Bu，Ph等）和底物范围（烷基，烯基和芳基）进行。生成的肼可通过氢解（阮内镍）的N–N键裂解或通过Li / NH 3的酰化和裂解而转化为胺。。通过改变取代基以包括更多的配位原子（氧和氮）以及去除配位原子，研究了侧链对非对映选择性的影响。带有2-甲氧基乙氧基甲基的SAMEMP助剂具有最高的非对映选择性。值得注意的是，带有简单甲基和异丁基取代基的助剂也具有很高的选择性。给出了选择性起源的假设。
• DENMARK, SCOTT E.;NICAISE, OLIVIER;EDWARDS, JAMES P., J. ORG. CHEM., 55,(1990) N5, C. 6219-6223
  作者：DENMARK, SCOTT E.、NICAISE, OLIVIER、EDWARDS, JAMES P.

  DOI：——

  日期：——
• Organocerium additions to hydrazones: effects of reagent stoichiometry on efficiency and selectivity
  作者：Scott E. Denmark、James P. Edwards、Olivier Nicaise

  DOI：10.1021/jo00055a008

  日期：1993.1

  The effects of reagent stoichiometry on the efficiency and selectivity of organocerium additions to chiral and achiral hydrazones have been investigated. rhe reagent formed in-situ from 1 equiv of CH3Li and 0.33 equiv of CeCl3 adds efficiently (>65% yield) to N,N-dimethylhydrazone 1, but this same reagent reacts only sluggishly with chiral SAMEMP hydrazone 2 (<30% yield). The optimal stoichiometry of the organocerium reagent is 1:1 CH3Li/CeCl3, despite the fact that not all of the CeCl3 ig consumed in the transmetalation. At least 2 equiv of methyl nucleophile is required to obtain acceptable yields in additions to 2, suggesting that the auxiliary side chain inhibits the reactivity of the first equivalent of organometallic reagent and that binding of the reagent to one of the hydrazone nitrogen atoms facilitates addition. This hypothesis is supported by the observation that competitive ligands such as amines or alkoxides effectively inhibit the addition of organocerium reagents to 1. The active reagent formed at all mixing stoichiometries is proposed to be a trimethyllanthanide species on the basis of reactivity and the presence of ur reacted MCl3 at less than 3:1 CH3Li/MCl3 mixing ratios.
• Lithium/ammonia cleavage of the nitrogen-nitrogen bond in N-(methoxycarbonyl)- and N-acetylhydrazines
  作者：Scott E. Denmark、Olivier Nicaise、James P. Edwards

  DOI：10.1021/jo00312a034

  日期：1990.12