(R)-ethyl 4-(tert-butoxycarbonylamino)-5-methylhexanoate | 494755-72-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (R)-ethyl 4-(tert-butoxycarbonylamino)-5-methylhexanoate
• 英文别名: ethyl (4S)-4-[N-(tert-butoxycarbonyl)amino]-5-methylhexanoate；Ethyl (R)-4-((tert-butoxycarbonyl)amino)-5-methylhexanoate；ethyl (4R)-5-methyl-4-[(2-methylpropan-2-yl)oxycarbonylamino]hexanoate
• CAS: 494755-72-5
• 化学式: C₁₄H₂₇NO₄
• 分子量: 273.373
• InChiKey: XXFLLEWETZSFNN-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-ethyl 4-(tert-butoxycarbonylamino)-5-methylhexanoate 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 ethyl (4R)-4-amino-5-methylhexanoate
  参考文献：
  名称：

  A Highly cis-Selective Synthesis of 2-Ethynylaziridines by Intramolecular Amination of Chiral Bromoallenes:  Improvement of Stereoselectivity Based on the Computational Investigation

  摘要：

  The base-mediated intramolecular amination of bromoallenes having an axial chirality is described. The treatment of (4S,aR)-4-alkyl-4-[N-(arylsulfonyl)amino]-1-bromobuta-1,2-dienes with NaH in DMF affords 2,3-cis-2-ethynylaziridines in good to excellent selectivity (2,3-cis:trans = 92:8-99:1). The reaction of (4S,aS)-bromoallenes with NaH/DMF also gives 2,3-cis-2-ethynylaziridines selectively (79:21-91:9). These experimental results have been rationalized by 133LYP density functional calculations together with the 6-31 +G(d) basis set and the Onsager solvation model. The transition structures for cis-aziridine formation of both (4S,aR)- and (4S,aS)-bromoallenes in DMF are favored over the corresponding trans transition structures by 4.35 and 1.41 kcal/mol, respectively. Furthermore, the calculations predicted that a less polar solvent gives higher cis selectivity for (4S,aS)-bromoallenes. In fact, improvement of the cis selectivity to 99:1 has been realized by using a less polar solvent such as THF. The cyclization of bromoallenes bearing a beta- or gamma-amino group also affords four- and five-membered azacycles in a highly cis-selective manner.

  DOI：

  10.1021/ja0262277
• 作为产物：
  描述：

  N-BOC-2(S)-2-AMINO-3-METHYL-BUTAL聽 在 palladium on activated charcoal 氢气 、 sodium hydride 作用下， 以 四氢呋喃 、 乙酸乙酯 为溶剂， 反应 5.67h， 生成 (R)-ethyl 4-(tert-butoxycarbonylamino)-5-methylhexanoate
  参考文献：
  名称：

  使用钯（0）/二乙基锌系统从带有溴原子的烯丙基醇衍生物合成丙二烯。

  摘要：

  描述了使用钯（0）/二乙基锌系统的通用且有效的丙二烯合成。在催化量的钯（0）存在下用二乙基锌处理（E）-或（Z）-2-溴代烷基-2-烯-1-醇的甲磺酸酯或三氯乙酸酯，得到带有氨基烷基，烷基或芳基的烯丙基良好或高收率的取代基。没有观察到手性从带有甲磺酰氧基的立体异构中心向丙二烯的转移。

  DOI：

  10.1021/jo016320y

文献信息

• 1-(2,4,6-Triisopropylphenyl)ethylamine:  A New Chiral Auxiliary for the Asymmetric Synthesis of γ-Amino Acid Derivatives
  作者：Pascale Cividino、Sandrine Py、Philippe Delair、Andrew E. Greene

  DOI：10.1021/jo061976i

  日期：2007.1.1

  The title compound has proven to be an excellent chiral auxiliary for nitrones in SmI2-mediated reductive coupling with α,β-unsaturated esters. A variety of such nitrones, prepared from aldehydes and enantiopure N-hydroxy-1-(2,4,6-triisopropylphenyl)ethylamine, afforded γ-N-hydroxyamino esters in high yields and diastereomeric purity. These adducts, readily available as either enantiomer, could be

  在SmI 2介导的与α，β-不饱和酯的还原偶联中，标题化合物被证明是硝酮的极好手性助剂。由醛和对映体纯的N-羟基-1-（2,4,6-三异丙基苯基）乙胺制得的多种此类硝酮以高收率和非对映体纯度提供了γ- N-羟基氨基酯。这些加合物，很容易以对映体的形式获得，可以转化为γ- N-乙酰氧基氨基酯，N -Boc-γ-氨基酯和γ-内酰胺。