(2S,3S,4E)-2--4-nonen-3-ol

• 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,3S,4E)-2--4-nonen-3-ol
• 英文别名: (E,2S,3S)-2-(benzhydrylideneamino)non-4-en-3-ol
• 化学式: C₂₂H₂₇NO
• 分子量: 321.462
• InChiKey: AYIZYJJCNXGDFY-MIUJDPCTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  32.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3S,4E)-2--4-nonen-3-ol 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 生成 (2S,3S,4E)-2-amino-4-nonen-3-ol
  参考文献：
  名称：

  Aluminoxy acetals from .alpha.-amino esters: chirality transfer via sequential addition of hydride and C-nucleophiles. 2-Amino alcohols and sphingosines

  摘要：

  The reaction of alpha-imino esters (O'Donnell's Schiff bases) with aluminum hydrides to produce acetal-like intermediates and subsequent reaction with carbon nucleophiles has been studied. Treatment of optically pure imine-protected amino esters with iBu2AlH or iBuAlH.Bu3Al, followed by RMgX or RLi provided threo-2-amino alcohols in high yield (73-85%) and excellent ''syn'' stereoselectivity (8:1 to >20.1, threo or like product preferred). Use of nonpolar solvents (CH2Cl2-hexane) provided the highest stereoselectivities. Use of the less-reactive iBu2AlH.iBu3Al complex lowered the amount of undesired primary alcohol products observed. Thermally labile aluminoxy acetal intermediates were observed by H-1 NMR and were trapped with N-(trimethylsilyl)imidazole to produce relatively stable monosilyl acetals (mixed acetals). Alanine-derived Schiff bases 2a-e showed a correlation between the steric bulk of the ester and threo selectivity The presence of THF reduced this correlation, suggesting the C-nucleophile addition involves a Lewis acid-assisted S(N)2-like displacement of the aluminoxy acetal or displacement of a tight-ion pair. In addition to the synthesis of optically pure arylethanolamines 6a-d from representative amino acids, threo-sphingosines 8a-d were synthesized from L-serine-derived Schiff base 4b, and 1-deoxy-threo-sphingosines 9a-d were synthesized from L-alanine in a similar fashion. Experimental details are provided.

  DOI：

  10.1021/jo00046a032
• 作为产物：
  描述：

  二苯甲酮亚胺 在 三异丁基铝 、 二异丁基氢化铝 作用下， 以 二氯甲烷 为溶剂， 反应 2.25h， 生成 (2S,3S,4E)-2--4-nonen-3-ol
  参考文献：
  名称：

  Aluminoxy acetals from .alpha.-amino esters: chirality transfer via sequential addition of hydride and C-nucleophiles. 2-Amino alcohols and sphingosines

  摘要：

  The reaction of alpha-imino esters (O'Donnell's Schiff bases) with aluminum hydrides to produce acetal-like intermediates and subsequent reaction with carbon nucleophiles has been studied. Treatment of optically pure imine-protected amino esters with iBu2AlH or iBuAlH.Bu3Al, followed by RMgX or RLi provided threo-2-amino alcohols in high yield (73-85%) and excellent ''syn'' stereoselectivity (8:1 to >20.1, threo or like product preferred). Use of nonpolar solvents (CH2Cl2-hexane) provided the highest stereoselectivities. Use of the less-reactive iBu2AlH.iBu3Al complex lowered the amount of undesired primary alcohol products observed. Thermally labile aluminoxy acetal intermediates were observed by H-1 NMR and were trapped with N-(trimethylsilyl)imidazole to produce relatively stable monosilyl acetals (mixed acetals). Alanine-derived Schiff bases 2a-e showed a correlation between the steric bulk of the ester and threo selectivity The presence of THF reduced this correlation, suggesting the C-nucleophile addition involves a Lewis acid-assisted S(N)2-like displacement of the aluminoxy acetal or displacement of a tight-ion pair. In addition to the synthesis of optically pure arylethanolamines 6a-d from representative amino acids, threo-sphingosines 8a-d were synthesized from L-serine-derived Schiff base 4b, and 1-deoxy-threo-sphingosines 9a-d were synthesized from L-alanine in a similar fashion. Experimental details are provided.

  DOI：

  10.1021/jo00046a032

文献信息

• Aluminoxy acetals from .alpha.-amino esters: chirality transfer via sequential addition of hydride and C-nucleophiles. 2-Amino alcohols and sphingosines
  作者：Robin Polt、Matt A. Peterson、Lynn DeYoung

  DOI：10.1021/jo00046a032

  日期：1992.9

  The reaction of alpha-imino esters (O'Donnell's Schiff bases) with aluminum hydrides to produce acetal-like intermediates and subsequent reaction with carbon nucleophiles has been studied. Treatment of optically pure imine-protected amino esters with iBu2AlH or iBuAlH.Bu3Al, followed by RMgX or RLi provided threo-2-amino alcohols in high yield (73-85%) and excellent ''syn'' stereoselectivity (8:1 to >20.1, threo or like product preferred). Use of nonpolar solvents (CH2Cl2-hexane) provided the highest stereoselectivities. Use of the less-reactive iBu2AlH.iBu3Al complex lowered the amount of undesired primary alcohol products observed. Thermally labile aluminoxy acetal intermediates were observed by H-1 NMR and were trapped with N-(trimethylsilyl)imidazole to produce relatively stable monosilyl acetals (mixed acetals). Alanine-derived Schiff bases 2a-e showed a correlation between the steric bulk of the ester and threo selectivity The presence of THF reduced this correlation, suggesting the C-nucleophile addition involves a Lewis acid-assisted S(N)2-like displacement of the aluminoxy acetal or displacement of a tight-ion pair. In addition to the synthesis of optically pure arylethanolamines 6a-d from representative amino acids, threo-sphingosines 8a-d were synthesized from L-serine-derived Schiff base 4b, and 1-deoxy-threo-sphingosines 9a-d were synthesized from L-alanine in a similar fashion. Experimental details are provided.