[2,2-Dimethyl-prop-(E)-ylidene]-((S)-2-methoxy-1-methyl-ethyl)-amine | 907189-19-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [2,2-Dimethyl-prop-(E)-ylidene]-((S)-2-methoxy-1-methyl-ethyl)-amine
• CAS: 907189-19-9
• 化学式: C₉H₁₉NO
• 分子量: 157.256
• InChiKey: PHICAQZHCLLARQ-VKHJRQFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.14
• 重原子数：
  11.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  21.59
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  正丁基锂 、 [2,2-Dimethyl-prop-(E)-ylidene]-((S)-2-methoxy-1-methyl-ethyl)-amine 在 四氢吡喃 、 N,N,N′,N′-tetramethylcyclohexane-1,2-diamine 作用下， 以 甲苯 为溶剂， 生成 ((S)-1-tert-Butyl-pentyl)-((S)-2-methoxy-1-methyl-ethyl)-amine 、 ((R)-1-tert-Butyl-pentyl)-((S)-2-methoxy-1-methyl-ethyl)-amine
  参考文献：
  名称：

  Structure of n-Butyllithium in Mixtures of Ethers and Diamines:  Influence of Mixed Solvation on 1,2-Additions to Imines

  摘要：

  n-BuLi in diamine/dialkyl ether mixtures forms ensembles of hetero- and homosolvated dimers. Solutions in TMEDA/THF (TMEDA = N, N, N', N'-tetramethylethylenediamine) are not amenable to detailed investigation because of rapid ligand exchange. TMCDA/THF mixtures (TMCDA = trans-N, N, N', N'-tetramethylcyclohexanediamine) afford clean assignments for a mixture of homo- and heterosolvated dimers but demonstrate poor control over structure. TMCDA/tetrahydropyran (THP) mixtures and TMEDA/Et2O mixtures afford clean structural assignments as well as excellent structural control. Rate studies of the 1,2-addition of n-BuLi using TMCDA/THP mixtures reveal cooperative solvation in which both THP and TMCDA coordinate to lithium at the monomer- and dimer-based transition structures. The two mechanisms are affiliated with markedly different stereochemistries of the 1,2-addition to imines. The results show strong parallels with previous investigations of 1,2-additions in TMEDA/Et2O mixtures.

  DOI：

  10.1021/ja0609654
• 作为产物：
  描述：

  特戊醛 、 (S)-(+)-1-甲氧基-2-丙胺 在 4 A molecular sieve 作用下， 反应 5.0h， 以75%的产率得到[2,2-Dimethyl-prop-(E)-ylidene]-((S)-2-methoxy-1-methyl-ethyl)-amine
  参考文献：
  名称：

  Addition of n-Butyllithium to an Aldimine:  Role of Chelation, Aggregation, and Cooperative Solvation

  摘要：

  Rate studies of the addition of n-BuLi in the presence of TMEDA to potentially chelating aldimines are consistent with a combination of monomer- and dimer-based mechanisms. Using mixtures of TMEDA and Et2O reveals cooperative solvation in which both Et2O and TMEDA coordinate to lithium at the monomer- and dimer-based transition structures. The four discrete mechanisms are affiliated with markedly different stereochemistries of the 1,2-addition.

  DOI：

  10.1021/ja0519987

文献信息

• A new α-selective synthetic equivalent for the crotyl anion in additions to imines
  作者：Johannes Betz、Manfred Heuschmann

  DOI：10.1016/0040-4039(95)00670-8

  日期：1995.6

  Two equivalents of vinylmagnesium bromide add to imines 1 in the presence of cerium trichloride to form homoallylic amines 3 as 2:1-adducts, Z-diastereomers being preferred by a margin of 88:12 to 71:29. Suitable chiral imines 1g-i are transformed to with high diastereoselectivity.

  在三氯化铈存在下，将两当量的乙烯基溴化镁加到亚胺1中，形成2：1加合物形式的均烯丙基胺3，Z-非对映异构体是优选的，边距为88:12至71:29。将合适的手性亚胺1g-i转化为具有高非对映选择性的化合物。