13²(S)-hydroxypheophorbide a methyl ester | 53358-14-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: 13²(S)-hydroxypheophorbide a methyl ester
• CAS: 53358-14-8；79733-03-2；92618-93-4
• 化学式: C₃₆H₃₈N₄O₆
• 分子量: 622.721
• InChiKey: DOFYAVLOCYRMIV-LOAKPLFLSA-N

物化性质

• 沸点：
  981.6±65.0 °C(Predicted)
• 密度：
  1.289±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.31
• 重原子数：
  46.0
• 可旋转键数：
  6.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  147.26
• 氢给体数：
  3.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  13²(S)-hydroxypheophorbide a methyl ester 在 过碘酸 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 20.0h， 生成 15¹(S)-hydroxypurpurin-7 lactone dimethyl ester 、 15¹(R)-hydroxypurpurin-7 lactone dimethyl ester
  参考文献：
  名称：

  Stereoselective Synthesis of New Chlorophyll a Related Antioxidants Isolated from Marine Organisms

  摘要：

  A new class of natural antioxidants, chlorophyll a related chlorins 3, 4(S), 4(R), 5(R), 6, 7, 8, and 9, have been synthesized from a chlorophyll a degradation product, pheophorbide a methyl ester (1). Claisen-type intramolecular condensation of pyropheophorbide a methyl ester (2) afforded the common intermediate enol 3. Chlorin 1 and enol 3 have a propensity to undergo exocyclic ring opening by ionic bases. The organic base DBU was found to be an efficient reagent for promoting the asymmetric hydroxylation of these chlorins, using N-sulfonyloxaziridines, without cleavage of the exocyclic rings. Model studies for hydroxylactonization have shown that periodate oxidation of hydroxy ketone 10 stereoselectively and predominantly forms hydroxy lactone 17(S). Periodate oxidation of alpha-hydroxy 1,3-diketone 4(R) and/or 4(S) to furnish hydroxy lactone 5(R) and diketone 7 was found out to be regioselective, and the site of reaction depends on the appropriate choice of reaction media. H-1 NMR spectra have provided information on the absolute configuration of diastereomers at the C-13(2) or C-15(1) position.

  DOI：

  10.1021/jo951854i
• 作为产物：
  描述：

  methylpheophorbide a 在 (1R)-(-)-(10-camphorsulfonyl)oxaziridine 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 生成 13²(R)-hydroxypheophorbide a methyl ester 、 13²(S)-hydroxypheophorbide a methyl ester
  参考文献：
  名称：

  Stereoselective Synthesis of New Chlorophyll a Related Antioxidants Isolated from Marine Organisms

  摘要：

  A new class of natural antioxidants, chlorophyll a related chlorins 3, 4(S), 4(R), 5(R), 6, 7, 8, and 9, have been synthesized from a chlorophyll a degradation product, pheophorbide a methyl ester (1). Claisen-type intramolecular condensation of pyropheophorbide a methyl ester (2) afforded the common intermediate enol 3. Chlorin 1 and enol 3 have a propensity to undergo exocyclic ring opening by ionic bases. The organic base DBU was found to be an efficient reagent for promoting the asymmetric hydroxylation of these chlorins, using N-sulfonyloxaziridines, without cleavage of the exocyclic rings. Model studies for hydroxylactonization have shown that periodate oxidation of hydroxy ketone 10 stereoselectively and predominantly forms hydroxy lactone 17(S). Periodate oxidation of alpha-hydroxy 1,3-diketone 4(R) and/or 4(S) to furnish hydroxy lactone 5(R) and diketone 7 was found out to be regioselective, and the site of reaction depends on the appropriate choice of reaction media. H-1 NMR spectra have provided information on the absolute configuration of diastereomers at the C-13(2) or C-15(1) position.

  DOI：

  10.1021/jo951854i

文献信息

• Nickel complexes of chlorophyll derivatives
  作者：D. V. Belykh、I. S. Tarabukina、Yu. S. Matveev、A. V. Kuchin

  DOI：10.1134/s1070363207070249

  日期：2007.7

  Nickel complexes of certain phorbine and amide derivatives of chlorophyll a were synthesized. Most of the chlorophyll a derivatives studied form nickel complexes when boiled in toluene with an equimolar amount of nickel acetylacetonate in high yield. The yields of the nickel complexes of the chlorophyll derivatives are determined by the stability of the starting ligand under the reaction conditions.
• Asymmetric hydroxylation of chlorophyll derivatives: A facile entry to both diastereomers of chlorophyllone a
  作者：Lifu Ma、David Dolphin

  DOI：10.1016/0957-4166(95)00001-6

  日期：1995.2

  High stereoselectivity is observed for the asymmetric oxidation of chlorophyll enolates derived from 13(2),17(3)-pheophorbide a enol (3), pheophorbide a methyl ester (8) and pheophytin a (9) with DBU and N-sulfonyl oxaziridines (4), (5) and (6).
• Cytotoxic Pheophorbide-Related Compounds from <i>Clerodendrum </i><i>c</i><i>alamitosum</i> and <i>C. cyrtophyllum</i>
  作者：Huey-Hwa Cheng、Hui-Kang Wang、Junko Ito、Kenneth F. Bastow、Yoko Tachibana、Yuka Nakanishi、Zhihong Xu、Tsui-Yun Luo、Kuo-Hsiung Lee

  DOI：10.1021/np000595b

  日期：2001.7.1

  Three pheophorbide-related compounds (1-3) were isolated from the leaves and stems of Clerodendrum calamitosum. The methyl ester of 3 (6) and the known (10S)-hydroxypheophytin a 7) also were isolated from leaves of the related plant Clerodendrum cyrtophyllum. Compounds 1 and 6 were isolated for the first time as naturally occurring products from a plant source. All structures were elucidated by detailed spectroscopic analysis. Biological evaluation showed that 1 and 2 exhibited strong cytotoxicity against human lung carcinoma (A549), ileocecal carcinoma (HCT-8), kidney carcinoma (CAKI-1), breast adenocarcinoma (MCF-7), malignant melanoma (SK-MEL-2), ovarian carcinoma (IA9), and epidermoid carcinoma of the nasopharynx (KB), and its etoposide- (KB-7d), vincristine- (KB-VCR), and camptothecin-resistant (KB-CPT) subclones. Compound 3 was less cytotoxic than 1 and 2. Compounds 4-6, the methyl esters of 1-3, showed strongly increased cytotoxicity compared with the parent acids. Interestingly, 6 was the most active derivative among these compounds. Compound 7 was inactive.