N-<4-(2,4,6-triisopropylbenzoyl)benzoyl>-(S)-phenylalanine methyl ester | 205311-39-3

• 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: N-<4-(2,4,6-triisopropylbenzoyl)benzoyl>-(S)-phenylalanine methyl ester
• 英文别名: methyl (2S)-3-phenyl-2-[[4-[2,4,6-tri(propan-2-yl)benzoyl]benzoyl]amino]propanoate
• CAS: 205311-39-3
• 化学式: C₃₃H₃₉NO₄
• 分子量: 513.677
• InChiKey: LWZRNAQCPBYQJE-LJAQVGFWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  38
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  72.5
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-<4-(2,4,6-triisopropylbenzoyl)benzoyl>-(S)-phenylalanine methyl ester 以 solid 为溶剂， 反应 15.0h， 以100%的产率得到N-<4-(7-hydroxy-3,5-diisopropyl-8,8-dimethylbicyclo<4.2.0>octa-1,3,5-trien-7-yl)benzoyl>-(S)-phenylalanine
  参考文献：
  名称：

  Crystal-to-Crystal Diastereoselective Transformation of 2,4,6-Triisopropyl-4'-(S)-phenylalaninocarbonylbenzophenone Methyl Ester

  摘要：

  通过在标题化合物{N-4-（2,4,6-三异丙基苯甲酰基）苯甲酰基]-(S)-苯丙氨酸甲酯 (I)} 中使用手性取代基(S)-甲基苯丙氨酸，诱导了光反应产物的不对称性。用 250 W 超高压汞灯的光通过长通滤光片照射晶体 7 小时后，晶体中的光反应 100% 完成，结晶度没有损失。X 射线衍射测定了光环化前的晶体结构（I）和光环化后的晶体结构（II）{N-[4-（7-羟基-3,5-二异丙基-8,8-二甲基双环[4.2.0]辛-1,3,5-三烯-7-基）苯甲酰基]-(S)-苯丙氨酸甲酯}。为了进行比较，我们还对 3′-COOMe衍生物重结晶后的光反应产物（III）{3-(7-羟基-3,5-二异丙基-8,8-二甲基双环[4.2.0]辛-1,3,5-三烯-7-基)苯甲酸甲酯}进行了晶体结构分析。在(I)中，中心羰基平面与三异丙基苯环之间的二面角偏离 90°，偏差达 10 (1)°，这使得位于 2 号和 6 号位置的异丙基的分子内 O（羰基）......H（甲基）距离不平衡。(II)的晶体结构表明，在反应中，距离较近的甲基 H 主要被羰基 O 原子抽取。产物环丁烯醇环中不对称 C 原子周围的绝对构型为 S。

  DOI：

  10.1107/s0108768198005503
• 作为产物：
  描述：

  4'-chloroformyl-2,4,6-triisopropylbenzophenone 在 sodium hydroxide 、 三乙胺 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 26.0h， 生成 N-<4-(2,4,6-triisopropylbenzoyl)benzoyl>-(S)-phenylalanine methyl ester
  参考文献：
  名称：

  Diastereoselective Photocyclization of N-(p-(2,4,6-Triisopropylbenzoyl)benzoyl)-l- phenylalanine Methyl Ester in the Solid State

  摘要：

  DOI：

  10.1021/jo980139g

文献信息

• Solid-State Photocyclization of 2,4,6-Triisopropyl-4‘-(methoxycarbonyl)benzophenone. Evidence for a Narrow Reaction Cavity and a Photoenol Diradical Intermediate
  作者：Yoshikatsu Ito、Satoshi Yasui、Jun Yamauchi、Shigeru Ohba、Gentaro Kano

  DOI：10.1021/jp973235e

  日期：1998.7.1

  The origin of the previously observed unusual photostability of 2,4,6-triisopropyl-4'-(methoxycarbonyl)benzophenone (1-p-CO2Me) in the solid state was investigated. 1-p-CO2Me was found to photocyclize normally to produce the corresponding benzocyclobutenol 2-p-CO2Me when its solid-state photolysis was carried out either (a) after thorough grinding, (b) after solid-solid mixing with 2,4,6-triisopropyl-4'-(ethoxycarbonyl)benzophenone (1-p-CO2Et), or (c) at elevated temperatures (an estimated energy barrier of 20 kcal/mol). Furthermore, when the photolysis was performed under more carefully deoxygenated conditions (closed argon atmosphere), formation of blue species that are persistent in the absence of oxygen was observed. On the basis of oxygen trapping and ESR experiments, the blue species are regarded as a mixture of a diradical intermediate DR and monoradicals derived thereof. The X-ray study of 1-p-CO2Me had revealed that the distances between the carbonyl oxygen and the o-i-Pr methine hydrogens are within the critical limit for hydrogen abstraction to occur, but a small reaction cavity or the compact crystal packing around both of the o-i-Pr groups is interfering with the photocyclization. The present results are consistent with this X-ray crystal structure; i.e., the photochemical hydrogen abstraction of 1-p-CO2Me to DR can take place, but DR reketonizes back to 1-p-CO2Me under the usual photolysis conditions because there is a high topochemical barrier to cyclization leading to 2-p-CO2Me.
• Diastereoselective Photocyclization of <i>N</i>-(<i>p</i>-(2,4,6-Triisopropylbenzoyl)benzoyl)-<scp>l</scp>- phenylalanine Methyl Ester in the Solid State
  作者：Yoshikatsu Ito、Gentaro Kano、Nobumasa Nakamura

  DOI：10.1021/jo980139g

  日期：1998.8.1
• Crystal-to-Crystal Diastereoselective Transformation of 2,4,6-Triisopropyl-4'-(<i>S</i>)-phenylalaninocarbonylbenzophenone Methyl Ester
  作者：H. Hosomi、Y. Ito、S. Ohba

  DOI：10.1107/s0108768198005503

  日期：1998.12.1

  Dissymmetry of the photoproduct was induced by using a chiral substituent, (S)-methylphenylalanine, in the title compound N-4-(2,4,6-triisopropylbenzoyl)benzoyl]-(S)-phenylalanine methyl ester (I)}. On irradiation with light from a 250 W ultra-high-pressure Hg lamp for 7 h through a long-pass filter, the photoreaction in a crystal was 100% complete without the loss of crystallinity. The crystal structures (I), before, and (II) N-[4-(7-hydroxy-3,5-diisopropyl-8,8-dimethylbicyclo[4.2.0]octa-1,3,5-trien-7-yl)benzoyl]-(S)-phenylalanine methyl ester}, after photocyclization, have been determined by X-ray diffraction. For comparison, a crystal structure analysis has also been carried out for the photoproduct (III) of the 3′-COOMe derivative after recrystallization methyl 3-(7-hydroxy-3,5-diisopropyl-8,8-dimethylbicyclo[4.2.0]octa-1,3,5-trien-7-yl)benzoate}. The dihedral angle between the central carbonyl plane and the triisopropylphenyl ring deviates from 90° by 10 (1)° in (I), which makes an imbalance in the intramolecular O(carbonyl)...H(methine) distances of the isopropyl groups at positions 2 and 6. The crystal structure of (II) indicates that the nearer methine H was predominantly abstracted by the carbonyl O atom in the reaction. The absolute configuration around the asymmetric C atom in the cyclobutenol ring of the product is S.

  通过在标题化合物N-4-（2,4,6-三异丙基苯甲酰基）苯甲酰基]-(S)-苯丙氨酸甲酯 (I)} 中使用手性取代基(S)-甲基苯丙氨酸，诱导了光反应产物的不对称性。用 250 W 超高压汞灯的光通过长通滤光片照射晶体 7 小时后，晶体中的光反应 100% 完成，结晶度没有损失。X 射线衍射测定了光环化前的晶体结构（I）和光环化后的晶体结构（II）N-[4-（7-羟基-3,5-二异丙基-8,8-二甲基双环[4.2.0]辛-1,3,5-三烯-7-基）苯甲酰基]-(S)-苯丙氨酸甲酯}。为了进行比较，我们还对 3′-COOMe衍生物重结晶后的光反应产物（III）3-(7-羟基-3,5-二异丙基-8,8-二甲基双环[4.2.0]辛-1,3,5-三烯-7-基)苯甲酸甲酯}进行了晶体结构分析。在(I)中，中心羰基平面与三异丙基苯环之间的二面角偏离 90°，偏差达 10 (1)°，这使得位于 2 号和 6 号位置的异丙基的分子内 O（羰基）......H（甲基）距离不平衡。(II)的晶体结构表明，在反应中，距离较近的甲基 H 主要被羰基 O 原子抽取。产物环丁烯醇环中不对称 C 原子周围的绝对构型为 S。