ditert-butyl (4aR,8aR)-2,6-bis(trifluoromethylsulfonyloxy)-4,4a,8,8a-tetrahydro-1,5-naphthyridine-1,5-dicarboxylate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: ditert-butyl (4aR,8aR)-2,6-bis(trifluoromethylsulfonyloxy)-4,4a,8,8a-tetrahydro-1,5-naphthyridine-1,5-dicarboxylate
• 化学式: C₂₀H₂₆F₆N₂O₁₀S₂
• 分子量: 632.556
• InChiKey: IANYCZGSMIHUAF-VXGBXAGGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  40
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  163
• 氢给体数：
  0
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  ditert-butyl (4aR,8aR)-2,6-bis(trifluoromethylsulfonyloxy)-4,4a,8,8a-tetrahydro-1,5-naphthyridine-1,5-dicarboxylate 在 bis-triphenylphosphine-palladium(II) chloride 、 sodium carbonate 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 32.5h， 生成 (9R,10R)-2,6-diphenyl-3,4,7,8,9,10-hexahydro-1,5-naphthyridine
  参考文献：
  名称：

  Conformational Control of Flexible Molecules:  Design and Synthesis of Novel Chiral 1,5-Diaza-cis-decalins

  摘要：

  Control of the conformational equilibria of 1,5-diaza-cis-decalins, a new class of chiral diamine ligands, has been investigated. Chiral 2,6- and 3,7-substituted derivatives of 1,5-diaza-cis-decalins were designed to stabilize the conformational form needed to chelate a lithium. These derivatives were synthesized in optically pure form starting from 1,5-diaza-cis-decalin. Due to the rigid and conformationally well-defined nature of these compounds, the potential of these compounds as chiral diamine ligands was investigated. Asymmetric lithiation-substitution reactions of N-Boc-pyrrolidine and N,N-diisopropyl-o-ethylbenzamide were performed using these ligands and up to 60% ee was obtained. For the latter substrate, results spanning a range from 32% ee (R) to 60% ee (S) were obtained (Deltaee = 92%) with 1,5-diaza-cis-decalin ligands differing only in the location of two methyl substituents. Unlike many other diamines that have been employed in asymmetric lithiation-substitution reactions, the limited conformational flexibility of the 1,5-diaza-cis-decalins is analogous to (-)-sparteine such that these results may permit the construction of structure-activity relationships.

  DOI：

  10.1021/jo025503x
• 作为产物：
  描述：

  (4aS,8aS)-Decahydro-[1,5]naphthyridine; compound with 2,3-dihydroxy-succinic acid 在 ruthenium(IV) oxide 、 sodium hydroxide 、 sodium periodate 、 lithium hexamethyldisilazane 作用下， 生成 ditert-butyl (4aR,8aR)-2,6-bis(trifluoromethylsulfonyloxy)-4,4a,8,8a-tetrahydro-1,5-naphthyridine-1,5-dicarboxylate
  参考文献：
  名称：

  1,5-二氮杂癸醛的异常氧化重排

  摘要：

  在用（PhIO）n或PhI（OAc）2处理后，1,5-二氮杂-顺式十氢化萘在更受阻的位置进行氧化，同时发生断裂，从而生成环扩展的比拉明。的顺式和反式1,5- diazadecalins都经历相同的消除指示用于氧化在多取代的碳氮的α位的电位立体电子偏好。在Boc保护的衍生物上完成了1,5-二氮杂-顺式十氢化萘的较低受阻位置的氧化，从而为合成2,6-取代的1,5,5-二氮杂-顺式十氢化萘提供了中间体。

  DOI：

  10.1016/s0040-4039(02)00559-2

文献信息

• Unusual oxidative rearrangement of 1,5-diazadecalin
  作者：Xiaolin Li、Zhenrong Xu、Erin F DiMauro、Marisa C Kozlowski

  DOI：10.1016/s0040-4039(02)00559-2

  日期：2002.5

  Upon treatment with (PhIO)n or PhI(OAc)2, 1,5-diaza-cis-decalin undergoes oxidation at the more hindered position along with fragmentation to yield the ring-expanded bislactam. The cis and trans 1,5-diazadecalins both undergo the same elimination indicating a potential stereoelectronic preference for oxidation at the more substituted carbon alpha to the nitrogen. Oxidation at the less hindered positions

  在用（PhIO）n或PhI（OAc）2处理后，1,5-二氮杂-顺式十氢化萘在更受阻的位置进行氧化，同时发生断裂，从而生成环扩展的比拉明。的顺式和反式1,5- diazadecalins都经历相同的消除指示用于氧化在多取代的碳氮的α位的电位立体电子偏好。在Boc保护的衍生物上完成了1,5-二氮杂-顺式十氢化萘的较低受阻位置的氧化，从而为合成2,6-取代的1,5,5-二氮杂-顺式十氢化萘提供了中间体。
• Conformational Control of Flexible Molecules:  Design and Synthesis of Novel Chiral 1,5-Diaza-<i>cis</i>-decalins
  作者：Zhenrong Xu、Marisa C. Kozlowski

  DOI：10.1021/jo025503x

  日期：2002.5.1

  Control of the conformational equilibria of 1,5-diaza-cis-decalins, a new class of chiral diamine ligands, has been investigated. Chiral 2,6- and 3,7-substituted derivatives of 1,5-diaza-cis-decalins were designed to stabilize the conformational form needed to chelate a lithium. These derivatives were synthesized in optically pure form starting from 1,5-diaza-cis-decalin. Due to the rigid and conformationally well-defined nature of these compounds, the potential of these compounds as chiral diamine ligands was investigated. Asymmetric lithiation-substitution reactions of N-Boc-pyrrolidine and N,N-diisopropyl-o-ethylbenzamide were performed using these ligands and up to 60% ee was obtained. For the latter substrate, results spanning a range from 32% ee (R) to 60% ee (S) were obtained (Deltaee = 92%) with 1,5-diaza-cis-decalin ligands differing only in the location of two methyl substituents. Unlike many other diamines that have been employed in asymmetric lithiation-substitution reactions, the limited conformational flexibility of the 1,5-diaza-cis-decalins is analogous to (-)-sparteine such that these results may permit the construction of structure-activity relationships.