2-bromo-N-methyl-N-[(1S)-1-phenylethyl]prop-2-en-1-amine | 204188-56-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2-bromo-N-methyl-N-[(1S)-1-phenylethyl]prop-2-en-1-amine
• CAS: 204188-56-7
• 化学式: C₁₂H₁₆BrN
• 分子量: 254.17
• InChiKey: LYQQCZNSARAZBS-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  14
• 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：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,3-二氢呋喃 、 (S)-(+)-alpha-甲氧基苯乙酸 、 3,4-二甲氧基-3-环丁烯-1,2-二酮 、 2-bromo-N-methyl-N-[(1S)-1-phenylethyl]prop-2-en-1-amine 生成 [(1S,5S,8S,11R)-8-hydroxy-10-methoxy-7-methylidene-2-oxatricyclo[6.3.0.01,5]undec-9-en-11-yl] (2S)-2-methoxy-2-phenylacetate 、 [(1R,5R,8R,11S)-8-hydroxy-10-methoxy-7-methylidene-2-oxatricyclo[6.3.0.01,5]undec-9-en-11-yl] (2S)-2-methoxy-2-phenylacetate
  参考文献：
  名称：

  1,5-Asymmetric Induction in Squarate Cascades. Conformational Control of Helicity by Chiral Amino Substituents during Conrotatory Octatetraene Cyclization Prior to β-Elimination

  摘要：

  Both the sigmatropic and electrocyclic rearrangement pathways that can arise when a pair of alkenyl anions are added to a squarate ester have high stereochemical demands. The distinction is nontrivial. When cis addition occurs initially, the stereoinduction that materializes at this point is fully transmitted into the product(s). The more commonly observed trans addition exhibits fleeting stereochemical consequences because of rapid equilibration of the octatetraenyl intermediates. In this instance, product distribution is governed by the relative rates of conrotatory cyclization at this advanced stage. Herein reported is a complete dissection of a squarate cascade when a stereogenic center attached to an amino substituent effects 1,5-asymmetric induction prior to B-elimination of the entire fragment. Deuterium labeling permits a direct measure of the contrasting kinetic imbalances associated with the two possible modes of alkenyl anion addition. Furthermore; quantitative analysis of the partitioning experienced by the two helical octatetraenes is readily accomplished. This work constitutes the first example where a complete dynamic profile for these complex processes has been possible. The fact that long-range asymmetric induction has been instrumental in solving the mechanistic puzzle is noteworthy.

  DOI：

  10.1021/jo9722921
• 作为产物：
  描述：

  (S)-methyl (1-phenylethyl)carbamate 在 lithium aluminium tetrahydride 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 2-bromo-N-methyl-N-[(1S)-1-phenylethyl]prop-2-en-1-amine
  参考文献：
  名称：

  1,5-Asymmetric Induction in Squarate Cascades. Conformational Control of Helicity by Chiral Amino Substituents during Conrotatory Octatetraene Cyclization Prior to β-Elimination

  摘要：

  Both the sigmatropic and electrocyclic rearrangement pathways that can arise when a pair of alkenyl anions are added to a squarate ester have high stereochemical demands. The distinction is nontrivial. When cis addition occurs initially, the stereoinduction that materializes at this point is fully transmitted into the product(s). The more commonly observed trans addition exhibits fleeting stereochemical consequences because of rapid equilibration of the octatetraenyl intermediates. In this instance, product distribution is governed by the relative rates of conrotatory cyclization at this advanced stage. Herein reported is a complete dissection of a squarate cascade when a stereogenic center attached to an amino substituent effects 1,5-asymmetric induction prior to B-elimination of the entire fragment. Deuterium labeling permits a direct measure of the contrasting kinetic imbalances associated with the two possible modes of alkenyl anion addition. Furthermore; quantitative analysis of the partitioning experienced by the two helical octatetraenes is readily accomplished. This work constitutes the first example where a complete dynamic profile for these complex processes has been possible. The fact that long-range asymmetric induction has been instrumental in solving the mechanistic puzzle is noteworthy.

  DOI：

  10.1021/jo9722921

文献信息

• 1,5-Asymmetric Induction in Squarate Cascades. Conformational Control of Helicity by Chiral Amino Substituents during Conrotatory Octatetraene Cyclization Prior to β-Elimination
  作者：Leo A. Paquette、Jinsung Tae

  DOI：10.1021/jo9722921

  日期：1998.3.1

  Both the sigmatropic and electrocyclic rearrangement pathways that can arise when a pair of alkenyl anions are added to a squarate ester have high stereochemical demands. The distinction is nontrivial. When cis addition occurs initially, the stereoinduction that materializes at this point is fully transmitted into the product(s). The more commonly observed trans addition exhibits fleeting stereochemical consequences because of rapid equilibration of the octatetraenyl intermediates. In this instance, product distribution is governed by the relative rates of conrotatory cyclization at this advanced stage. Herein reported is a complete dissection of a squarate cascade when a stereogenic center attached to an amino substituent effects 1,5-asymmetric induction prior to B-elimination of the entire fragment. Deuterium labeling permits a direct measure of the contrasting kinetic imbalances associated with the two possible modes of alkenyl anion addition. Furthermore; quantitative analysis of the partitioning experienced by the two helical octatetraenes is readily accomplished. This work constitutes the first example where a complete dynamic profile for these complex processes has been possible. The fact that long-range asymmetric induction has been instrumental in solving the mechanistic puzzle is noteworthy.