H4EsterB* | 743478-67-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酰胺类
• 英文名称: H4EsterB*
• 英文别名: Methyl 4,4,7,7,10,10-hexamethyl-3,6,8,11-tetraoxo-2,5,9,12-tetrazabicyclo[11.4.0]heptadeca-1(13),14,16-triene-15-carboxylate；methyl 4,4,7,7,10,10-hexamethyl-3,6,8,11-tetraoxo-2,5,9,12-tetrazabicyclo[11.4.0]heptadeca-1(13),14,16-triene-15-carboxylate
• CAS: 743478-67-3
• 化学式: C₂₁H₂₈N₄O₆
• 分子量: 432.477
• InChiKey: KMSBTZSHUCFQOJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  31
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  143
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  H4EsterB* 在 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 正庚烷 、 乙基苯 为溶剂， 反应 5.17h， 生成
  参考文献：
  名称：

  Enantioselective Hydroxylation of Benzylic C(sp³)–H Bonds by an Artificial Iron Hydroxylase Based on the Biotin–Streptavidin Technology

  摘要：

  The selective hydroxylation of C-H bonds is of great interest to the synthetic community. Both homogeneous catalysts and enzymes offer complementary means to tackle this challenge. Herein, we show that biotinylated Fe(TAML)-complexes (TAML = Tetra Amido Macrocyclic Ligand) can be used as cofactors for incorporation into streptavidin to assemble artificial hydroxylases. Chemo-genetic optimization of both cofactor and streptavidin allowed optimizing the performance of the hydroxylase. Using H2O2 as oxidant, up to similar to 300 turnovers for the oxidation of benzylic C-H bonds were obtained. Upgrading the ee was achieved by kinetic resolution of the resulting benzylic alcohol to afford up to >98% ee for (R)-tetralol. X-ray analysis of artificial hydroxylases highlights critical details of the second coordination sphere around the Fe(TAML) cofactor.

  DOI：

  10.1021/jacs.0c02788
• 作为产物：
  描述：

  在 肼 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 生成 H4EsterB*
  参考文献：
  名称：

  一种用于不对称自由基型氧原子转移催化的Co(TAML)基人工金属酶

  摘要：

  我们证明，在链霉亲和素中掺入生物素化 Co(TAML) 辅因子能够实现不对称自由基型氧原子转移催化，并提高活性和对映选择性。

  DOI：

  10.1039/d3cc04723g

文献信息

• Synthesis of macrocyclic tetraamido compounds and new metal insertion process
  申请人：——

  公开号：US20040167329A1

  公开（公告）日：2004-08-26

  An improved method of synthesizing a macrocyclic tetraamido compound includes protecting the amino portion of an amino carboxylic acid to form a protected amino carboxylic acid; exposing the protected amino carboxylic acid to a first solvent, preferably a hydrocarbon solvent, such as toluene or 1,2-dichloroethane, dichloromethane, dibromomethane and 1,2-dibromoethane. The carboxylic acid portion of the protected amino carboxylic acid is then converted to an activated carboxylic acid by one of esterification or acid halide formation, to form a protected amino activated carboxylic acid derivative. The protected amino activated carboxylic acid derivative is reacted with a diamine in the presence of a second solvent, such as THF or ,2-dichloroethane, dichloromethane, dibromomethane and 1,2-dibromoethane, to form a protected diamide diamine intermediate. Following deprotection, the diamide diamine intermediate is reacted with an activated diacid, such as an activated malonate, oxalate or succinate derivative to form the macrocyclic tetraamido compound. The macrocyclic tetraamido compound may further be complexed with a transition metal.

  一种改进的合成大环四酰胺化合物的方法，包括保护氨基羧酸的氨基部分以形成受保护的氨基羧酸；将受保护的氨基羧酸暴露于第一种溶剂中，优选为烃类溶剂，例如甲苯或1,2-二氯乙烷、二氯甲烷、二溴甲烷和1,2-二溴乙烷。然后，通过酯化或酸卤化形成将受保护的氨基羧酸转化为活化羧酸，以形成受保护的氨基活化羧酸衍生物。在第二种溶剂的存在下，例如THF或2-二氯乙烷、二氯甲烷、二溴甲烷和1,2-二溴乙烷，将受保护的氨基活化羧酸衍生物与二胺反应，以形成受保护的二酰胺二胺中间体。经去保护后，将二酰胺二胺中间体与活化二酸，例如活性丙二酸酯、草酸酯或琥珀酸酯衍生物反应，以形成大环四酰胺化合物。大环四酰胺化合物可以进一步与过渡金属络合。
• Enantioselective Hydroxylation of Benzylic C(sp³)–H Bonds by an Artificial Iron Hydroxylase Based on the Biotin–Streptavidin Technology
  作者：Joan Serrano-Plana、Corentin Rumo、Johannes G. Rebelein、Ryan L. Peterson、Maxime Barnet、Thomas R. Ward

  DOI：10.1021/jacs.0c02788

  日期：2020.6.17

  The selective hydroxylation of C-H bonds is of great interest to the synthetic community. Both homogeneous catalysts and enzymes offer complementary means to tackle this challenge. Herein, we show that biotinylated Fe(TAML)-complexes (TAML = Tetra Amido Macrocyclic Ligand) can be used as cofactors for incorporation into streptavidin to assemble artificial hydroxylases. Chemo-genetic optimization of both cofactor and streptavidin allowed optimizing the performance of the hydroxylase. Using H2O2 as oxidant, up to similar to 300 turnovers for the oxidation of benzylic C-H bonds were obtained. Upgrading the ee was achieved by kinetic resolution of the resulting benzylic alcohol to afford up to >98% ee for (R)-tetralol. X-ray analysis of artificial hydroxylases highlights critical details of the second coordination sphere around the Fe(TAML) cofactor.