(-)-1-[(1R)-1-(3,4-dimethoxybenzoyl)-2-methoxy-1-methyl-2-oxoethyl]-1,2-hydrazinedicarboxylic acid 1,2-di-tert-butylester | 1281895-24-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-1-[(1R)-1-(3,4-dimethoxybenzoyl)-2-methoxy-1-methyl-2-oxoethyl]-1,2-hydrazinedicarboxylic acid 1,2-di-tert-butylester
• 英文别名: (R)-di-tert-butyl 1-(1-(3,4-dimethoxyphenyl)-3-methoxy-2-methyl-1,3-dioxopropan-2-yl)hydrazine-1,2-dicarboxylate；(R)-(-)-di-tert-butyl 1-[1-(3,4-dimethoxybenzoyl)-1-(methoxycarbonyl)ethyl]-1,2-hydrazinedicarboxylate
• CAS: 1281895-24-6
• 化学式: C₂₃H₃₄N₂O₉
• 分子量: 482.531
• InChiKey: SHKGCVJBMYSREC-HSZRJFAPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  34.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  129.7
• 氢给体数：
  1.0
• 氢受体数：
  9.0

反应信息

• 作为产物：
  描述：

  3,4-二甲氧基苯乙酮 在 sodium hydride 、 potassium carbonate 、 europium(III) trifluoromethanesulfonate 、 2,6-二[(4S)-4-苯基-2-恶唑啉基]吡啶 作用下， 以 四氢呋喃 、 丙酮 、 乙腈 、 mineral oil 为溶剂， 反应 30.5h， 生成 (S)-di-tert-butyl 1-(1-(3,4-dimethoxyphenyl)-3-methoxy-2-methyl-1,3-dioxopropan-2-yl)hydrazine-1,2-dicarboxylate 、 (-)-1-[(1R)-1-(3,4-dimethoxybenzoyl)-2-methoxy-1-methyl-2-oxoethyl]-1,2-hydrazinedicarboxylic acid 1,2-di-tert-butylester
  参考文献：
  名称：

  Asymmetric Synthesis of l-Carbidopa Based on a Highly Enantioselective α-Amination

  摘要：

  A stereoselective synthesis of L-carbidopa in seven steps and 50% overall yield from commercial compounds is described. The key step involves a highly enantloselective alpha-amlnation reaction of an acyclic beta-ketoester with di-tert-butyl azodicarboxylate induced by europium and (R,R)-dlphenyl-pybox.

  DOI：

  10.1021/ol400136y

文献信息

• Chiral lithium binaphtholate for enantioselective amination of acyclic α-alkyl-β-keto esters: Application to the total synthesis of l-carbidopa
  作者：Toshifumi Asano、Miyuki Moritani、Makoto Nakajima、Shunsuke Kotani

  DOI：10.1016/j.tet.2017.08.015

  日期：2017.10

  A chiral lithium binaphtholate catalyzes the enantioselective amination of α-alkyl-β-keto esters with azodicarboxylates to produce optically active α,α-disubstituted α-amino acid derivatives in high yields and with good to high enantioselectivities. A stoichiometric amount of lithium hydroxide efficaciously improved both the reactivity and enantioselectivity of amination. The resulting aminated product

  手性双萘二甲酸锂催化α-烷基-β-酮酯与偶氮二羧酸酯的对映选择性胺化，以高收率和良好至高对映选择性地制备光学活性的α，α-二取代的α-氨基酸衍生物。化学计量的氢氧化锂有效地改善了胺化的反应性和对映选择性。所得胺化产物易于转化为1-卡比多巴。
• Enantioselective amination of acyclic α-alkylated β-keto esters catalyzed by chiral lithium binaphtholate
  作者：Shunsuke Kotani、Toshifumi Asano、Miyuki Moritani、Makoto Nakajima

  DOI：10.1016/j.tetlet.2016.08.013

  日期：2016.9

  The enantioselective amination of α-alkylated β-keto esters with azodicarboxylates using a chiral dilithium binaphtholate as catalyst affords optically active α,α-disubstituted α-amino acid derivatives in high enantioselectivities of up to 95% ee. A stoichiometric amount of lithium hydroxide accelerates the amination. This method provides easy access to various chiral α,α-disubstituted α-amino acids

  使用手性联萘二酸二锂锂作为催化剂，用偶氮二羧酸酯对α-烷基化的β-酮酯进行对映选择性胺化，可得到光学活性的α，α-二取代的α-氨基酸衍生物，其对映体选择性高达95％ee。化学计量的氢氧化锂促进了胺化。该方法可容易地从容易获得的起始原料和手性来源中以高收率和高对映选择性获得各种手性α，α-二取代的α-氨基酸。