tert-butyl (2S,4R)-6-azido-2-[(tert-butoxycarbonyl)amino]-4-{[tert-butyl(diphenyl)silyl]oxy}hexanoate | 653589-54-9

• 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: tert-butyl (2S,4R)-6-azido-2-[(tert-butoxycarbonyl)amino]-4-{[tert-butyl(diphenyl)silyl]oxy}hexanoate
• 英文别名: (2S,4R)-tert-butyl 6-azido-2-(tert-butoxycarbonylamino)-4-(tert-butyldiphenylsilyloxy)hexanoate
• CAS: 653589-54-9
• 化学式: C₃₁H₄₆N₄O₅Si
• 分子量: 582.816
• InChiKey: BQQKVYYCPLOLAA-BVAGGSTKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.26
• 重原子数：
  41.0
• 可旋转键数：
  11.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  122.62
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  tert-butyl (2S,4R)-6-azido-2-[(tert-butoxycarbonyl)amino]-4-{[tert-butyl(diphenyl)silyl]oxy}hexanoate 在 potassium carbonate 、 三氟乙酸 作用下， 以 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 3.0h， 生成 (2S,4R)-6-azido-4-{[tert-butyl(diphenyl)silyl]oxy}-2-{[(9H-fluoren-9-ylmethoxy)carbonyl]amino}hexanoic acid
  参考文献：
  名称：

  Synthesis of Enantiopure 4-Hydroxypipecolate and 4-Hydroxylysine Derivatives from a Common 4,6-Dioxopiperidinecarboxylate Precursor

  摘要：

  tert-Butyl 2-substituted 4,6-dioxo-1-piperidinecarboxylates 4 have been prepared in good yield starting from Boc-Asp-(OBu)-Bu-t and other beta-amino acids. By analogy with chiral tetramic acids, their reduction by NaBH4 in CH2Cl2/AcOH afforded the corresponding cis-4-hydroxy delta-lactams in good yield and stereoselectivity (68-98% de). In the absence of the A(1,3) strain (reduction of 6-substituted 2,4-dioxo-1-piperidines 7), the cis-4-hydroxy isomer was still obtained as the major product but the de values were consistently lower. 4-Hydroxy-6-oxo-1,2-piperidinedicarboxylate 2a, readily accessible from Boc-Asp-OtBu (three steps, 63% overall yield), has proven to be an excellent building block for the synthesis of cis- and trans-4-hydroxypipecolates 17 and 24 (52 and 36% overall yield, respectively) and for the synthesis of a protected 4-hydroxylysine derivative 29 (41% overall yield).

  DOI：

  10.1021/jo0353886
• 作为产物：
  描述：

  di(tert-butyl) (2S,4S)-4-{[tert-butyl(diphenyl)silyl]oxy}-6-oxo-1,2-piperidinedicarboxylate 在 sodium tetrahydroborate 、 sodium azide 、 N,N-二异丙基乙胺 作用下， 以 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 11.0h， 生成 tert-butyl (2S,4R)-6-azido-2-[(tert-butoxycarbonyl)amino]-4-{[tert-butyl(diphenyl)silyl]oxy}hexanoate
  参考文献：
  名称：

  Synthesis of Enantiopure 4-Hydroxypipecolate and 4-Hydroxylysine Derivatives from a Common 4,6-Dioxopiperidinecarboxylate Precursor

  摘要：

  tert-Butyl 2-substituted 4,6-dioxo-1-piperidinecarboxylates 4 have been prepared in good yield starting from Boc-Asp-(OBu)-Bu-t and other beta-amino acids. By analogy with chiral tetramic acids, their reduction by NaBH4 in CH2Cl2/AcOH afforded the corresponding cis-4-hydroxy delta-lactams in good yield and stereoselectivity (68-98% de). In the absence of the A(1,3) strain (reduction of 6-substituted 2,4-dioxo-1-piperidines 7), the cis-4-hydroxy isomer was still obtained as the major product but the de values were consistently lower. 4-Hydroxy-6-oxo-1,2-piperidinedicarboxylate 2a, readily accessible from Boc-Asp-OtBu (three steps, 63% overall yield), has proven to be an excellent building block for the synthesis of cis- and trans-4-hydroxypipecolates 17 and 24 (52 and 36% overall yield, respectively) and for the synthesis of a protected 4-hydroxylysine derivative 29 (41% overall yield).

  DOI：

  10.1021/jo0353886

文献信息

• Synthesis of K48-linked diubiquitin using dual native chemical ligation at lysine
  作者：Renliang Yang、Kalyan Kumar Pasunooti、Fupeng Li、Xue-Wei Liu、Chuan-Fa Liu

  DOI：10.1039/c0cc01382j

  日期：——

  The dual native chemical ligation at lysine strategy was revised by replacing the acid-labile Cbz protecting group with photolabile NVOC at the 4-mercaptolysine side chain. The optimized strategy was subsequently applied to the synthesis of K48-linked diubiquitin.

  通过在4巯基赖氨酸侧链上用光不稳定的NVOC取代对酸不稳定的Cbz保护基，修订了在赖氨酸策略上的双重天然化学连接。随后将优化的策略应用于K48连接的双泛素的合成。
• Synthesis of 4-mercapto-l-lysine derivatives: Potential building blocks for sequential native chemical ligation
  作者：Kalyan Kumar Pasunooti、Renliang Yang、Seenuvasan Vedachalam、Bala Kishan Gorityala、Chuan-Fa Liu、Xue-Wei Liu

  DOI：10.1016/j.bmcl.2009.09.107

  日期：2009.11

  A general and diastereoselective synthesis of (2S, 4S)-4-mercapto-l-lysine derivative was described. The key features of this synthesis include Zn-mediated diastereoselective Reformatsky reaction and selective reduction of methyl ester with sodium borohydride. Introduction of thiol functional group on lysine side chain proved to be appropriate for dual native chemical ligation. This methodology allows

  描述了（2 S，4 S）-4-巯基-1-赖氨酸衍生物的一般和非对映选择性合成。该合成的关键特征包括锌介导的非对映选择性Reformatsky反应和用硼氢化钠选择性还原甲酯。赖氨酸侧链上硫醇官能团的引入被证明适用于双重天然化学连接。该方法学允许开发各种4-取代的1-赖氨酸衍生物。
• Dual Native Chemical Ligation at Lysine
  作者：Renliang Yang、Kalyan Kumar Pasunooti、Fupeng Li、Xue-Wei Liu、Chuan-Fa Liu

  DOI：10.1021/ja905491p

  日期：2009.9.30

  A thiol group introduced on the gamma-carbon of lysine mediates robust native chemical Ligation at both the alpha- and epsilon-amines in two consecutive steps. Desulfurization then affords the final product, in which the lysine residue at the ligation site has an isopeptide bond on its side chain. The method is useful for the synthesis of proteins containing special post-translational modifications on lysine.