6-((perfluorophenoxy)carbonyl)naphthalen-2-yl (1R,5S,7s)-1,5,7-trimethyl-2,4-dioxo-3-azabicyclo[3.3.1]nonane-7-carboxylate | 124650-87-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 6-((perfluorophenoxy)carbonyl)naphthalen-2-yl (1R,5S,7s)-1,5,7-trimethyl-2,4-dioxo-3-azabicyclo[3.3.1]nonane-7-carboxylate
• CAS: 124650-87-9
• 化学式: C₂₉H₂₂F₅NO₆
• 分子量: 575.489
• InChiKey: APRDUKKOYDVSCS-PKQPGRETSA-N

物化性质

• 沸点：
  709.1±60.0 °C(Predicted)
• 密度：
  1.441±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.52
• 重原子数：
  41.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  98.77
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  6-((perfluorophenoxy)carbonyl)naphthalen-2-yl (1R,5S,7s)-1,5,7-trimethyl-2,4-dioxo-3-azabicyclo[3.3.1]nonane-7-carboxylate 、 5-氨基-5-脱氧-2,3-O-(1-甲基亚乙基)-腺苷酸 在 三乙胺 作用下， 以 氯仿 为溶剂， 反应 24.0h， 以92%的产率得到
  参考文献：
  名称：

  Rebek 自我复制系统的动力学分析：是否存在争议？

  摘要：

  1 和 2 的 Rebek 自复制反应，由两种反应物与所得产物 3 络合催化（Tjivikua, T.；等人 J. Am. Chem. Soc. 1990, 112, 1249-1250. Nowick, JS ; et al. J. Am. Chem. Soc. 1991, 113, 8831-8839. Wintner, EA; et al. Acc. Chem. Res. 1994, 27, 198-203. Conn, MM; et al. J. Am. Chem. Soc. 1994, 116, 8823-8824)，以及 Menger 等人的相关工作。(Menger, FM; et al. J. Am. Chem. Soc. 1994, 116, 3613-3614. Menger, FM; et al. J. Org. Chem. 1995, 60, 2870-2878) 已

  DOI：

  10.1021/ja960324g
• 作为产物：
  描述：

  2-羟基-6-萘甲酸 在 吡啶 、 盐酸 、 4-二甲氨基吡啶 、 氯化亚砜 、 碳酸氢钠 、 三乙胺 、 N,N-二甲基甲酰胺 作用下， 以 甲醇 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 36.0h， 生成 6-((perfluorophenoxy)carbonyl)naphthalen-2-yl (1R,5S,7s)-1,5,7-trimethyl-2,4-dioxo-3-azabicyclo[3.3.1]nonane-7-carboxylate
  参考文献：
  名称：

  Kinetic studies and modeling of a self-replicating system

  摘要：

  The design, synthesis, and study of a molecular template, 11a, that catalyzes its own formation from simpler components, 9 and 10d, is described. Autocatalysis is shown by the following: (1) the increase in rate of reaction of 9 and 10d in the presence of lla; (2) the reduction in rate of reaction in the presence of 2,6-bis(acetylamino)pyridine inhibitor; and (3) the reduction in rate of reaction when a component incapable of template behavior, 10h, is substituted for 10d. Three kinetic pathways are elucidated: (1) the background bimolecular reaction (eq 6); (2) the preassociative mechanism (eq 7); and (3) the template termolecular process (eq 8). A kinetic model for the replication process is introduced, and equilibrium and rate constants are determined. Predictions for the shapes of the product growth curves are made.

  DOI：

  10.1021/ja00023a036

文献信息

• Evidence for an Alternative Mechanism to a Previously Proposed Self-Replicating System
  作者：F. M. Menger、A. V. Eliseev、N. A. Khanjin、M. J. Sherrod

  DOI：10.1021/jo00114a043

  日期：1995.5

  Rebek et al.(1,2) have proposed a ''self-replicative'' mechanism in which the amide product of an ester aminolysis forms a termolecular complex with the ester and amine reactants. In this manner, the product catalyzes its own formation. The evidence for the mechanism lies mainly in a 40-70% acceleration when product is added externally to the reaction mixture. The system has now been reinvestigated owing, in part, to doubts created by troublesome experimental problems (e.g. small rate enhancements coupled to greater than or equal to 35% unidentified side reactions) and by the entropic unlikelihood of the highly constrained termolecular complex. Our new experiments prove that the Rebek mechanism is unnecessary. Thus, the aminolysis of simple naphthoyl and benzoyl esters, both lacking any hydrogen-bonding sites, are catalyzed by the Rebek ''template''. In the latter case, the reactions were run under the identical conditions used recently by Rebek (2 mM) while monitoring the formation of the major reaction product. Although the benzoyl ester cannot hydrogen-bond to the template, the ester aminolysis is catalyzed by the template to an extent even greater than that observed by Rebek (i.e. 2-fold). The Rebek mechanism, predicated upon ester/template binding, is clearly invalidated by these experiments. An alternative mechanism, involving amide catalysis, is proposed and found consistent with all available data.
• "A Self-Replicating System": New Experimental Data and a New Mechanistic Interpretation
  作者：F. M. Menger、Alexey V. Eliseev、Nikolai A. Khanjin

  DOI：10.1021/ja00087a063

  日期：1994.4
• Evidence against an Alternative Mechanism for a Self-Replicating System
  作者：Edward A. Wintner、Belinda Tsao、Julius Rebek

  DOI：10.1021/jo00129a046

  日期：1995.12

  A recent paper by Menger et al. described experimental and computational work related to our self-replicating system and concluded that amide catalysis-either external or internal-is the cause of observed rate enhancements. Herein we show that the proposal of Menger et al. is inconsistent with published data, that their conclusions overreach the data afforded by their experiments, and that the step which they modeled is likely irrelevant to the autocatalytic nature of the system. We present new results and a refined mechanism in which the transition state is stabilized not by amides but by template-based recognition, the hallmark of self-replicating systems.
• Tjivikua; Ballester; Rebek Jr., Journal of the American Chemical Society, 1990, vol. 112, # 3, p. 1249 - 1250
  作者：Tjivikua、Ballester、Rebek Jr.

  DOI：——

  日期：——
• New Evidence for Template Effects in a Self-Replicating System
  作者：M. Morgan Conn、Edward A. Wintner、J. Rebek

  DOI：10.1021/ja00098a058

  日期：1994.9