4-amino-2-methyl-2-butanol | 141649-03-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-amino-2-methyl-2-butanol
• 英文别名: 2-methyl-4-[[(1S)-1-phenylethyl]amino]butan-2-ol
• CAS: 141649-03-8
• 化学式: C₁₃H₂₁NO
• 分子量: 207.316
• InChiKey: OAMKHXLUFCQTLD-NSHDSACASA-N

物化性质

• 沸点：
  312.9±25.0 °C(Predicted)
• 密度：
  0.978±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  32.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-amino-2-methyl-2-butanol 在 copper(l) iodide 、 正丁基锂 、 三乙胺 作用下， 以 四氢呋喃 、 甲苯 、 正戊烷 为溶剂， 反应 0.5h， 生成 (S)-(1'''l,2l,3''u)-(1'E)-2-<3'-(3''-Oxocyclopentyl)-1'-propenyl>-6,6-dimethyl-3-(1-phenylethyl)-1,3,2-oxazaphosphorinane 2-oxide
  参考文献：
  名称：

  Asymmetric Michael Addition Reaction of Phosphorus-Stabilized Allyl Anions with Cyclic Enones

  摘要：

  The asymmetric Michael addition reaction of chirally modified P-allyl anions derived from enantiomerically enriched 2-allyl-1,3,2-oxazaphosphorinane 2-oxides has been investigated with cyclic enones. The racemic 1,3,2-oxazaphosphorinane 2-oxide 3 has been shown to be extremely diastereoselective in the Michael addition to 5-, 6-, and 7-ring enones. With the enantiomerically enriched 2-allyl-1,3,2-oxazaphosphorinane 2-oxides, high regio- and diastereoselectivities (88-90% diastereomeric excess) have been achieved in the Michael addition reaction of one of the diastereomers (cis series). The Michael reaction of the anions derived from the trans series were not diastereoselective (similar to 10% diastereomeric excess). The origin of the addition selectivity can be rationalized by (1) consideration of the structure and conformational preferences of the allyl anion (parallel conformation, s-trans, no lithium contact), (2) conformational analysis of the 1,3,2-oxazaphosphorinane 2-oxide ring (chair, equatorial allyl group) and (3) assumption of a 10-membered ring transition state structure with lithium coordination of the enone.

  DOI：

  10.1021/jo00128a028

文献信息

• Asymmetric electrophilic amination of chiral phosphorus-stabilized anions
  作者：Scott E. Denmark、Naoto Chatani、Sunil V. Pansare

  DOI：10.1016/s0040-4020(01)88883-9

  日期：1992.1

  The asymmetric electrophilic amination of phosphorus-stabilized anions derived from chiral oxazaphosphorinanes and diazaphospholidines is described. Trisyl azide is the reagent of choice for the amination process. The reaction is shown to be dependent on auxiliary structure, nature of the P-alkyl substituent and choice of amination procedure. Using the oxazaphosphorinanes 1a and cis-1e a high level

  描述了衍生自手性氧杂氮磷腈和二氮磷吡啶的磷稳定阴离子的不对称亲电胺化反应。三叠氮化物是胺化过程的首选试剂。已表明该反应取决于辅助结构，对-烷基取代基的性质和胺化方法的选择。使用草氮磷膦酸酯1a和cis-1e可以实现高水平的不对称诱导。在（S）对映体中，Scalemic cis-1e提供具有92％ee的α-氨基膦酸13。讨论了构象和辅助结构对立体选择性的影响。
• Asymmetric Michael Addition Reaction of Phosphorus-Stabilized Allyl Anions with Cyclic Enones
  作者：Scott E. Denmark、Jung-Ho Kim

  DOI：10.1021/jo00128a028

  日期：1995.11

  The asymmetric Michael addition reaction of chirally modified P-allyl anions derived from enantiomerically enriched 2-allyl-1,3,2-oxazaphosphorinane 2-oxides has been investigated with cyclic enones. The racemic 1,3,2-oxazaphosphorinane 2-oxide 3 has been shown to be extremely diastereoselective in the Michael addition to 5-, 6-, and 7-ring enones. With the enantiomerically enriched 2-allyl-1,3,2-oxazaphosphorinane 2-oxides, high regio- and diastereoselectivities (88-90% diastereomeric excess) have been achieved in the Michael addition reaction of one of the diastereomers (cis series). The Michael reaction of the anions derived from the trans series were not diastereoselective (similar to 10% diastereomeric excess). The origin of the addition selectivity can be rationalized by (1) consideration of the structure and conformational preferences of the allyl anion (parallel conformation, s-trans, no lithium contact), (2) conformational analysis of the 1,3,2-oxazaphosphorinane 2-oxide ring (chair, equatorial allyl group) and (3) assumption of a 10-membered ring transition state structure with lithium coordination of the enone.