(S)-2-methyl-N-(1-phenylethyl)prop-2-en-1-amine

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (S)-2-methyl-N-(1-phenylethyl)prop-2-en-1-amine
• 英文别名: (S)-N-(α-methylbenzyl)methallylamine；2-methyl-N-[(1S)-1-phenylethyl]prop-2-en-1-amine
• 化学式: C₁₂H₁₇N
• 分子量: 175.274
• InChiKey: RFCBRLQSZIUFCG-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-2-methyl-N-(1-phenylethyl)prop-2-en-1-amine 在 四(三苯基膦)钯 、 二甲基硫 、 三苯基硼烷 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 48.5h， 生成 2-(3-methyl-2-oxo-1-((S)-1-phenylethyl)azetidin-3-yl)acetonitrile
  参考文献：
  名称：

  烯烃的非对映选择性分子内氰基酰胺化

  摘要：

  本文报道了非对映选择性分子内烯烃氰基酰胺化，其中手性导向基团赋予高 dr 值。具有α-全碳四元立体中心的内酰胺很容易合成，这可能使我们能够获得在生物活性分子和天然产物中常见的结构。

  DOI：

  10.1002/ejoc.201601283
• 作为产物：
  描述：

  3-溴-2-甲基丙烯 、 (S)-(-)- α-甲基苄胺 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以89%的产率得到(S)-2-methyl-N-(1-phenylethyl)prop-2-en-1-amine
  参考文献：
  名称：

  Loss of Chirality through Facile Lewis Base Mediated Aza-enolate Formation in Na and K (S)-N-(α-Methylbenzyl)methallylamides

  摘要：

  Metalation of (S)-N-(alpha-methylbenzyl)-methallylamine with nBuM (M = Li, Na, or K) in hexane leads to the allylic metal amides [(S)-PhCH(CH3)N(CH2C-{CH3}=CHLi)Li](6), 1, [(S)-PhCH(CH3)N(CH2C{CH3}-= CH2)Na](n), and [(S)-PhCH(CH3)N(CH2C{CH3}=CH2)K](n), respectively. The addition of any Lewis base (here THF, TMEDA, or PMDETA) to the Na and K amides promotes rapid anion rearrangement to the aza-enolate complexes [PhC(=CH2)N(CH2CH{CH3}(2))Na](infinity), 2, [PhC(=CH2)N-(CH2CH{CH3}(2))Na center dot TMEDA](n), 3, [PhC(=CH2)N(CH2CH-{CH3}(2))Na center dot PMDETA](n), 4, and [PhC(=CH2)N(CH2CH-{CH3}(2))K](n), 5, resulting in loss of chirality. In contrast, the addition of benzene leads exclusively to the 1-aza-allyl complexes [(S)-PhCH(CH3)N(CH=C{CH3}(2))Na](n), 6, and [(S)-PhCH(CH3)N(CH=C{CH3}(2))K](n), 7, not observed in the presence of Lewis donors. Doping a benzene solution of 7 with THF gives the first observation of reorganization to the intermediate 2-aza-allyl anion. All seven complexes have been characterized by NMR spectroscopy, with complexes 1 and 2 also being characterized by single-crystal X-ray diffraction. Rearrangement to the aza-enolates 2 and 3 is unprecedented under the conditions employed.

  DOI：

  10.1021/acs.organomet.6b00445

文献信息

• α,γ-Dioxygenated amides via tandem Brook rearrangement/radical oxygenation reactions and their application to syntheses of γ-lactams
  作者：Mikhail K Klychnikov、Radek Pohl、Ivana Císařová、Ullrich Jahn

  DOI：10.3762/bjoc.17.58

  日期：——

  N-allylic silylacetamides and TEMPO is reported. The sequence starts with a new tandem nucleophilic substitution/Brook rearrangement/single electron transfer-induced radical oxygenation furnishing orthogonally protected α,γ-dioxygenated N-allylamides with wide scope, mostly good yields, and partly good diastereo- and enantioselectivity for defined combinations of chiral epoxides and chiral amides

  吡咯烷酮是各种生物活性化合物中常见的杂环片段。在此，报道了一种基于两步自由基的方法，从环氧化物、 N-烯丙基甲硅烷基乙酰胺和 TEMPO 开始制备带有三到四个立构中心的 γ-内酰胺。该序列以新的串联亲核取代/布鲁克重排/单电子转移诱导的自由基氧化开始，提供正交保护的α,γ-二氧化N-烯丙基酰胺，其范围广，产率大多良好，并且对于确定的组合具有部分良好的非对映和对映选择性手性环氧化物和手性酰胺。这代表了羰基旁边氧化孪晶 C-C/C-O 双官能化的非常罕见的例子。所得二氧化烯丙酰胺随后进行基于持久自由基效应的5-外-三自由基环化反应，以高产率提供作为非对映体混合物的官能化吡咯烷酮。它们通过碱基介导的平衡聚合成 3,4-反式-γ-内酰胺，可以轻松地进一步多样化。开发了两种反应类型的立体化学模型。
• Diastereoselective Intramolecular Cyanoamidation with Alkenes
  作者：Ashley M. Dreis、Sadie C. Otte、Matthew S. Eastwood、Elizabeth R. Alonzi、Jason T. Brethorst、Christopher J. Douglas

  DOI：10.1002/ejoc.201601283

  日期：2017.1.3

  Reported herein is a diastereoselective intramolecular alkene cyanoamidation, wherein high d.r. values are imparted by chiral directing groups. Lactams with an α-all-carbon quaternary stereocenter are readily synthesized, which may enable access to structures frequently found in biologically active molecules and natural products.

  本文报道了非对映选择性分子内烯烃氰基酰胺化，其中手性导向基团赋予高 dr 值。具有α-全碳四元立体中心的内酰胺很容易合成，这可能使我们能够获得在生物活性分子和天然产物中常见的结构。
• Loss of Chirality through Facile Lewis Base Mediated Aza-enolate Formation in Na and K (<i>S</i>)-<i>N</i>-(α-Methylbenzyl)methallylamides
  作者：Matthew T. Flynn、Rachel Stott、Victoria L. Blair、Philip C. Andrews

  DOI：10.1021/acs.organomet.6b00445

  日期：2016.8.22

  Metalation of (S)-N-(alpha-methylbenzyl)-methallylamine with nBuM (M = Li, Na, or K) in hexane leads to the allylic metal amides [(S)-PhCH(CH3)N(CH2C-CH3}=CHLi)Li](6), 1, [(S)-PhCH(CH3)N(CH2CCH3}-= CH2)Na](n), and [(S)-PhCH(CH3)N(CH2CCH3}=CH2)K](n), respectively. The addition of any Lewis base (here THF, TMEDA, or PMDETA) to the Na and K amides promotes rapid anion rearrangement to the aza-enolate complexes [PhC(=CH2)N(CH2CHCH3}(2))Na](infinity), 2, [PhC(=CH2)N-(CH2CHCH3}(2))Na center dot TMEDA](n), 3, [PhC(=CH2)N(CH2CH-CH3}(2))Na center dot PMDETA](n), 4, and [PhC(=CH2)N(CH2CH-CH3}(2))K](n), 5, resulting in loss of chirality. In contrast, the addition of benzene leads exclusively to the 1-aza-allyl complexes [(S)-PhCH(CH3)N(CH=CCH3}(2))Na](n), 6, and [(S)-PhCH(CH3)N(CH=CCH3}(2))K](n), 7, not observed in the presence of Lewis donors. Doping a benzene solution of 7 with THF gives the first observation of reorganization to the intermediate 2-aza-allyl anion. All seven complexes have been characterized by NMR spectroscopy, with complexes 1 and 2 also being characterized by single-crystal X-ray diffraction. Rearrangement to the aza-enolates 2 and 3 is unprecedented under the conditions employed.