(S)-4-(tert-Butyl-dimethyl-silanyloxy)-2,5-dimethyl-3-oxo-hexanoic acid benzyl ester | 185515-75-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-4-(tert-Butyl-dimethyl-silanyloxy)-2,5-dimethyl-3-oxo-hexanoic acid benzyl ester
• 英文别名: (4S)-Benzyl 4-((tert-butyldimethylsilyl)oxy)-2,5-dimethyl-3-oxohexanoate；benzyl (4S)-4-[tert-butyl(dimethyl)silyl]oxy-2,5-dimethyl-3-oxohexanoate
• CAS: 185515-75-7
• 化学式: C₂₁H₃₄O₄Si
• 分子量: 378.584
• InChiKey: NKHQRXFTODIREL-CVMIBEPCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.98
• 重原子数：
  26
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-4-(tert-Butyl-dimethyl-silanyloxy)-2,5-dimethyl-3-oxo-hexanoic acid benzyl ester 在 tetrabutylammonium tetrafluoroborate 作用下， 以 四氢呋喃 为溶剂， 反应 0.75h， 以47%的产率得到(4S)-4-Isopropyl-2-methyltetronic acid
  参考文献：
  名称：

  Synthesis of derivatives of (2S,4S)-4-hydroxy-2,5-dimethyl-3-oxohexanoic acid, a constituent of the didemnins

  摘要：

  The syntheses of the two protected derivatives 7 and 16 of (2S,4S)-4-hydroxy-2, 5-dimethyl-3-oxohexanoic acid, a constituent of the didemnin family of antineoplastic macrocyclic depsipeptides are described, The preparation of 7 was carried out by modification of a previously reported synthetic route whereas the use of derivative 16 represents a novel approach to the management of this sub-unit, Removal of the carboxy protecting groups from 7 or 16, followed by amide bond formation with derivatives of(S)-leucine, and oxidation in the cases of compounds deriving from 16, generates the diastereoisomeric intermediates 11, 22 and 23, In each of these either of the protecting groups can be removed in the presence of the other, allowing them to be elaborated further at either terminus, Previous work indicates that diastereoisomeric mixtures of such intermediates can, in principle, be used to obtain optically pure didemnins.

  DOI：

  10.1039/p19960001427
• 作为产物：
  描述：

  L-α-羟基异戊酸 在 咪唑 、 potassium carbonate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 50.83h， 生成 (S)-4-(tert-Butyl-dimethyl-silanyloxy)-2,5-dimethyl-3-oxo-hexanoic acid benzyl ester
  参考文献：
  名称：

  Synthesis of derivatives of (2S,4S)-4-hydroxy-2,5-dimethyl-3-oxohexanoic acid, a constituent of the didemnins

  摘要：

  The syntheses of the two protected derivatives 7 and 16 of (2S,4S)-4-hydroxy-2, 5-dimethyl-3-oxohexanoic acid, a constituent of the didemnin family of antineoplastic macrocyclic depsipeptides are described, The preparation of 7 was carried out by modification of a previously reported synthetic route whereas the use of derivative 16 represents a novel approach to the management of this sub-unit, Removal of the carboxy protecting groups from 7 or 16, followed by amide bond formation with derivatives of(S)-leucine, and oxidation in the cases of compounds deriving from 16, generates the diastereoisomeric intermediates 11, 22 and 23, In each of these either of the protecting groups can be removed in the presence of the other, allowing them to be elaborated further at either terminus, Previous work indicates that diastereoisomeric mixtures of such intermediates can, in principle, be used to obtain optically pure didemnins.

  DOI：

  10.1039/p19960001427

文献信息

• Total Synthesis of Dehydrodidemnin B. Use of Uronium and Phosphonium Salt Coupling Reagents in Peptide Synthesis in Solution
  作者：Gemma Jou、Isabel González、Fernando Albericio、Paul Lloyd-Williams、Ernest Giralt

  DOI：10.1021/jo961932h

  日期：1997.1.1

  (R)-N(Me)-Leu. Deprotection of the amino and carboxyl terminii of this linear precursor followed by macrocyclization gave a protected derivative of didemnin A. The second route involved synthesis of the Boc-protected didemnin macrocycle from a linear hexadepsipeptide lacking (R)-N(Me)-Leu. Removal of the Boc group from the macrocycle followed by its coupling with Boc-(R)-N(Me)-Leu-OH then gave Boc-didemnin A

  描述了二氢肌动蛋白A和脱氢肌苷B的新的总合成。在该大环二肽家族的所有成员中，后者的双氢精蛋白具有最高的抗增殖活性。它是通过将Pyr-Pro-OH侧链与双精胺A偶联而制得的，而双精胺A本身是通过两种新途径合成的。其中一个是基于线性直链的七肽肽的精制而成，该肽掺入了双氢精蛋白侧链的第一个氨基酸（R）-N（Me）-Leu。对该线性前体的氨基和羧基末端进行脱保护，然后进行大环化，得到了双联蛋白A的保护衍生物。第二种方法涉及从缺少（R）-N（Me）-Leu的线性六肽中合成Boc保护的双联蛋白大环。从大环中除去Boc基团，然后将其与Boc-（R）-N（Me）-Leu-OH偶联，得到Boc-地精A。第二种策略的总收率要高得多（27％比4 （对于第一次合成，％），但是两者都允许制备与天然样品相同的合成二氢肌酐A。大量使用了基于phospho和铀盐的偶联剂，例如BOP，PyBrOP，PyAOP，HBTU和H
• Synthesis of derivatives of (2S,4S)-4-hydroxy-2,5-dimethyl-3-oxohexanoic acid, a constituent of the didemnins
  作者：Isabel González、Gemma Jou、Josep Maria Caba、Fernando Albericio、Paul Lloyd-Williams、Ernest Giralt

  DOI：10.1039/p19960001427

  日期：——

  The syntheses of the two protected derivatives 7 and 16 of (2S,4S)-4-hydroxy-2, 5-dimethyl-3-oxohexanoic acid, a constituent of the didemnin family of antineoplastic macrocyclic depsipeptides are described, The preparation of 7 was carried out by modification of a previously reported synthetic route whereas the use of derivative 16 represents a novel approach to the management of this sub-unit, Removal of the carboxy protecting groups from 7 or 16, followed by amide bond formation with derivatives of(S)-leucine, and oxidation in the cases of compounds deriving from 16, generates the diastereoisomeric intermediates 11, 22 and 23, In each of these either of the protecting groups can be removed in the presence of the other, allowing them to be elaborated further at either terminus, Previous work indicates that diastereoisomeric mixtures of such intermediates can, in principle, be used to obtain optically pure didemnins.