人血草碱 | 84-39-9

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 原小檗碱生物碱及其衍生物
• 中文名称: 人血草碱
• 中文别名: 金罂粟碱
• 英文名称: (S)-stylopine
• 英文别名: stylopine；l-stylopine；(1S)-5,7,17,19-tetraoxa-13-azahexacyclo[11.11.0.02,10.04,8.015,23.016,20]tetracosa-2,4(8),9,15(23),16(20),21-hexaene
• CAS: 84-39-9
• 化学式: C₁₉H₁₇NO₄
• 分子量: 323.348
• InChiKey: UXYJCYXWJGAKQY-HNNXBMFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  40.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  人血草碱 、 碘甲烷 以77%的产率得到
  参考文献：
  名称：

  KULKARNI, B. K.;DHAR, R. K.;DE, SOUZA N. J., J. HETEROCYCL. CHEM., 27,(1990) N, C. 623-626

  摘要：

  DOI：
• 作为产物：
  描述：

  金黄紫堇碱 在 enzyme 作用下， 生成 人血草碱
  参考文献：
  名称：

  Formation of both methylenedioxy groups in the alkaloid (S)-stylopine is catalyzed by cytochrome P-450 enzymes

  摘要：

  DOI：

  10.1016/s0040-4039(01)93756-6

文献信息

• Development of a Fully Continuous‐Flow Approach Towards Asymmetric Total Synthesis of Tetrahydroprotoberberine Natural Alkaloids
  作者：Weijian Li、Meifen Jiang、Minjie Liu、Xu Ling、Yingqi Xia、Li Wan、Fener Chen

  DOI：10.1002/chem.202200700

  日期：2022.6.10

  A fully continuous flow approach towards asymmetric total synthesis of four natural tetrahydroprotoberberine alkaloids, was developed through a concise linear sequence involving four chemical transformations and three on-line work-up processes without any intermediate purification. The overall yields and enantioselectivities obtained in this novel integrated flow platform were up to 50 % and 92 %ee

  通过涉及四个化学转化和三个在线后处理过程的简洁线性序列开发了一种完全连续流动的方法，用于不对称全合成四种天然四氢原小檗碱生物碱，无需任何中间纯化。在这种新型集成流动平台中获得的总产率和对映选择性分别高达 50% 和 92% ee，总停留时间为 32.5 分钟。
• Characterization of two methylenedioxy bridge-forming cytochrome P450-dependent enzymes of alkaloid formation in the Mexican prickly poppy Argemone mexicana
  作者：Maria Luisa Díaz Chávez、Megan Rolf、Andreas Gesell、Toni M. Kutchan

  DOI：10.1016/j.abb.2010.11.016

  日期：2011.3

  2-month-old plantlets of the Mexican prickly poppy Argemone mexicana that accumulated the benzo[c]phenanthridine alkaloid sanguinarine and the protoberberine alkaloid berberine. CYP719A13 and CYP719A14 are 58% identical to each other and 77% and 60% identical, respectively, to stylopine synthase CYP719A2 of benzo[c]phenanthridine biosynthesis in Eschscholzia californica. Functional heterologous expression of

  亚甲基二氧基桥的形成是在罂粟科植物中生物合成苯并[c]菲啶和原小ine碱生物碱中不可或缺的步骤。植物中的该反应被细胞色素P450依赖性酶催化。在对一个由两个月大的墨西哥仙人掌罂粟Argemone mexicana的小植株制备的EST数据集进行查询后，鉴定出两个编码CYP719家族的细胞色素P450酶的cDNA，它们积累了苯并[c]菲啶生物碱sanguinarine和原小ber碱生物碱小ber碱。CYP719A13和CYP719A14与加利福尼亚州大肠埃希菌中苯并[c]菲啶生物合成的苯乙烯类合成酶CYP719A2彼此相同，分别为58％和77％和60％。在草地贪夜蛾Sf9细胞中CYP719A14和CYP719A13的功能异源表达产生了重组酶，分别催化了（S）-苦瓜碱和（S）-甜菊碱的（S）-甜菜碱和（S）-甜菊碱的亚甲二氧基桥的形成。 。每种酶测试了27种潜在的底物。而CYP719A14仅将（
• Molecular cloning and characterization of methylenedioxy bridge-forming enzymes involved in stylopine biosynthesis in<i>Eschscholzia californica</i>
  作者：Nobuhiro Ikezawa、Kinuko Iwasa、Fumihiko Sato

  DOI：10.1111/j.1742-4658.2007.05652.x

  日期：2007.2

  involved in stylopine biosynthesis were isolated using degenerate primers designed for C. japonica CYP719 from cultured Eschscholzia californica cells. Heterologous expression in Saccharomyces cerevisiae showed that both CYP719A2 and CYP719A3 had stylopine synthase activity to catalyze methylenedioxy bridge-formation from cheilanthifoline to stylopine, but not cheilanthifoline synthase activity to convert

  （S）-斯蒂洛平是苯并菲啶生物碱如血红碱的生物合成中的重要中间体。stylopine的生物合成涉及两个亚甲基二氧基桥的顺序形成。尽管已从黄连中克隆了与小ber碱生物合成有关的形成亚甲二氧基桥的P450（CYP719）[Ikezawa N，Tanaka M，Nagayoshi M，Shinkyo R，Sakaki T，Inouye K＆Sato F（2003）J Biol Chem278，38557- 38565]，尚无有关苯乙烯类生物合成中亚甲二氧基桥形成酶基因的信息。使用从日本埃森氏菌（Eschscholzia californica）培养的日本粳稻CYP719设计的简并引物，分离出两个与苯乙烯类生物合成有关的细胞色素P450 cDNA。酿酒酵母中的异源表达表明CYP719A2和CYP719A3均具有苯乙烯平合酶活性来催化从Cheilanthifoline到stylopine的亚甲二氧基
• Gadamer, Sitzungsberichte der Gesellschaft zur Befoerderung der Gesamten Naturwissenschaften zu Marburg, 1927, vol. 62, p. 156
  作者：Gadamer

  DOI：——

  日期：——
• Isolation and characterization of a cDNA encoding (S)-cis-N-methylstylopine 14-hydroxylase from opium poppy, a key enzyme in sanguinarine biosynthesis
  作者：Guillaume A.W. Beaudoin、Peter J. Facchini

  DOI：10.1016/j.bbrc.2012.12.129

  日期：2013.2

  Sanguinarine is a benzo[c]phenenthridine alkaloid with potent antimicrobial properties found commonly in plants of the Papaveraceae, including the roots of opium poppy (Papaver somniferum). Sanguinarine is formed from the central 1-benzylisoquinoline intermediate (S)-reticuline via the protoberberine alkaloid (S)-scoulerine, which undergoes five enzymatic oxidations and an N-methylation. The first four oxidations from (S)-scoulerine are catalyzed by cytochromes P450, whereas the final conversion involves a flavoprotein oxidase. All but gine gene in the biosynthetic pathway from (S)-reticuline to sanguinarine has been identified. In this communication, we report the isolation and characterization of (S)-cis-N-methylstylopine 14-hydroxylase (MSH) from opium poppy based on the transcriptional induction in elicitor-treated cell suspension cultures and root-specific expression of the corresponding gene. Along with protopine 6-hydroxylase, which catalyzes the subsequent and penultimate step in sanguinarine biosynthesis, MSH is a member of the CYP82N subfamily of cytochromes P450. The full-length MSH cDNA was expressed in Saccharomyces cerevisiae and the recombinant microsomal protein was tested for enzymatic activity using 25 benzylisoquinoline alkaloids representing a wide range of structural subgroups. The only enzymatic substrates were the N-methylated protoberberine alkaloids N-methylstylopine and N-methylcanadine, which were converted to protopine and allocryptopine, respectively. (C) 2013 Published by Elsevier Inc.