xylapyrroside B | 1337989-98-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: xylapyrroside B
• 英文别名: (2S,4S,5R)-4-hydroxy-5-(hydroxymethyl)-1',4,4',5-tetrahydro-3H-spiro[furan-2,3'-pyrrolo-[2,1-c][1,4]oxazine]-6'-carbaldehyde；shensongine B；(3S,4'S,5'R)-4'-hydroxy-5'-(hydroxymethyl)spiro[1,4-dihydropyrrolo[2,1-c][1,4]oxazine-3,2'-oxolane]-6-carbaldehyde
• CAS: 1337989-98-6
• 化学式: C₁₂H₁₅NO₅
• 分子量: 253.255
• InChiKey: XTXCPGDPIWDLPP-TUAOUCFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  80.9
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1H-吡咯-2,5-二甲醛 在 盐酸 、 sodium tetrahydroborate 、 4-甲基苯磺酸吡啶 、 戴斯-马丁氧化剂 、 potassium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 55.5h， 生成 xylapyrroside B
  参考文献：
  名称：

  Xylapyrrosides A and B, two rare sugar-morpholine spiroketal pyrrole-derived alkaloids from Xylaria nigripes: isolation, complete structure elucidation, and total syntheses

  摘要：

  Two new [named xylapyrrosides A (1) and B (2)1 along with two known [pollenopyrrosides A (3) and B (=acortatarin A, 4)] naturally occurring spirocyclic pyrrole alkaloids were isolated and identified as minor components from the Et0H extract of the dried mycelia of the edible medicinal fungus Xylaria nigripes. Their structures were established by a combination of interpretation of spectroscopic data and single-crystal X-ray diffraction analyses. The isolates possess a unique tricyclic skeleton comprising a common bicyclic 2-formyl-pyrrole-fused morpholine, with a variable ketohexoside ring. This class of alkaloids is quite rare from natural sources. In this study, the total syntheses of compounds 1, 2 and 4 were successfully achieved by two alternative strategies, and three new analogs [named xylapyrrosides A(1) (1a), A(2) (1b) and B-1 (2a)] were also produced. Notably, the total synthesis of such spiroketal alkaloids with a pyranose ring (e.g.,1) was accomplished for the first time. The absolute configurations of the new isolates can be thereafter unequivocally secured by the total syntheses. The above isolated and synthesized spiro-alkaloids were found to show moderate antioxidant effects by preventing the oxidative stress-induced cytotoxicity of A7r5 rat vascular smooth muscle cells (VSMCs). (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.06.020

文献信息

• Zeolite-Based Organic Synthesis (ZeoBOS) of Acortatarin A: First Total Synthesis Based on Native and Metal-Doped Zeolite-Catalyzed Steps
  作者：Eric Wimmer、Sophie Borghèse、Aurélien Blanc、Valérie Bénéteau、Patrick Pale

  DOI：10.1002/chem.201605048

  日期：2017.1.31

  Similarly to polymer‐supported assisted synthesis (PSAS), organic synthesis could be envisaged being performed by using zeolites, native or metal‐doped, as heterogeneous catalysts. To illustrate this unprecedented Zeolite‐Based Organic Synthesis (ZeoBOS), the total synthesis of acortatarin A was achieved through a novel strategy and using five out of eleven synthetic steps catalyzed by H‐ or metal‐doped

  与聚合物支持的辅助合成（PSAS）相似，可以设想通过使用天然或掺杂金属的沸石作为多相催化剂进行有机合成。为了说明这种史无前例的基于沸石的有机合成（ZeoBOS），通过一种新颖的策略并使用了H或金属掺杂的沸石催化的11个合成步骤中的5个作为催化剂，完成了鹰嘴豆素A的全合成。值得注意的是，与铜掺杂的沸石形成炔吡咯中间体和与银掺杂的沸石对炔二醇的螺缩合反应已被开发为合成的关键步骤。
• A Convergent Synthesis of the 2-Formylpyrrole Spiroketal Natural Product Acortatarin A
  作者：Margaret Brimble、Hui Geng、Jack Chen、Daniel Furkert、Shende Jiang

  DOI：10.1055/s-0031-1290508

  日期：2012.4

  flexible synthesis of the morpholine-spiroketal natural product acortatarin A, isolated from the traditional Chinese medicine Acorus tatarinowii, is reported. The key step involves a Maillard-type condensation of an amine derived from d -mannitol with a dihydropyranone. The approach also enables access to analogues of acortatarin A for biological evaluation and can be applied to the synthesis of related

  报道了从中药蒺藜中分离的吗啉-螺酮天然产物 acortatarin A 的简洁灵活的合成方法。关键步骤涉及衍生自 d-甘露醇的胺与二氢吡喃酮的美拉德型缩合。该方法还能够获得用于生物学评价的 acortatarin A 类似物，并可应用于相关 2-甲酰基吡咯天然产物的合成。
• Synthesis of the Revised Structure of Acortatarin A
  作者：Hui Min Geng、Louise A. Stubbing、Jack Li-yang Chen、Daniel P. Furkert、Margaret A. Brimble

  DOI：10.1002/ejoc.201403000

  日期：2014.10

  dihydropyranone, was used as a key step to access the unusual morpholine-spiroketal acortatarin A. The synthetic approach also enabled access to a C-2 analogue of acortatarin A, and can be used for the synthesis of related 2-formylpyrrole natural products.

  衍生自 D-甘露醇的伯胺与二氢吡喃酮之间的新型美拉德型缩合被用作获得不寻常的吗啉-螺旋酮醇 Acortatarin A 的关键步骤。该合成方法还能够获得 acortatarin A 的 C-2 类似物，可用于合成相关的2-甲酰基吡咯天然产物。
• Total Synthesis and Stereochemical Revision of Acortatarins A and B
  作者：Gangarajula Sudhakar、Vilas D. Kadam、Shruthi Bayya、Gavinolla Pranitha、Bharatam Jagadeesh

  DOI：10.1021/ol202121k

  日期：2011.10.21

  A first total synthesis of acortatarins A, B, and an enantiomer of the proposed structure of acortatarin B is described by using readily available d-sugars. This convergent total synthesis revealed the revision of the absolute configuration of acortatarin A and structural revision of acortatarin B. The key steps involved are regioselective epoxide opening with deprotonated 2,5-disubstituted pyrrole

  通过使用容易获得的d-糖描述了第一步的全合成的角蛋白A，B和对映体结构的对映体。这种聚合的总合成揭示了对阿考塔林A的绝对构型的修订和对阿考塔林B的结构的修订。涉及的关键步骤是用去质子化的2，5-二取代的吡咯进行的区域选择性环氧化物的开环和螺缩酮化。
• Taste-Active Maillard Reaction Products in Roasted Garlic (<i>Allium sativum</i>)
  作者：Junichiro Wakamatsu、Timo D. Stark、Thomas Hofmann

  DOI：10.1021/acs.jafc.6b02396

  日期：2016.7.27

  In order to gain first insight into candidate Maillard reaction products formed upon thermal processing of garlic, mixtures of glucose and S-allyl-l-cysteine, the major sulfur-containing amino acid in garlic, were low-moisture heated, and nine major reaction products were isolated. LC-TOF-MS, 1D/2D NMR, and CD spectroscopy led to their identification as acortatarin A (1), pollenopyrroside A (2), epi-acortatarin

  为了初步了解大蒜热处理后形成的候选美拉德反应产物，将葡萄糖和大蒜中主要的含硫氨基酸S-烯丙基-1-半胱氨酸的混合物进行了低水分加热，并进行了九次主要反应产品被分离。LC-TOF-MS，一维/二维NMR，和CD光谱导致他们识别为acortatarin A（1），pollenopyrroside A（2），外延-acortatarin A（3），xylapyrroside A（4），5-羟甲基-1- -[[（5-羟甲基-2-呋喃基）甲基] -1 H-吡咯-2-羰基-氢化物（5），3-（烯丙基硫基）-2-（2-甲酰基-5-羟甲基-1 H-吡咯-1-基）丙酸（6），（4 S）-4-（烯丙基硫代甲基）-3,4-二氢-3-氧代-1 H-吡咯并[2,1- c ] [1,4]恶嗪-6-甲醛（7），（2 R）-3-（烯丙基硫基）-2-[（（4 R）-4-（烯丙基硫基甲基）-6-甲酰基-3-氧代-3,4-二氢吡咯并-[1