4-甲氧基-6-[(1R,2S,4aR,8aR)-2-甲基-1,2,4a,5,6,7,8,8a-八氢-1-萘基]-2-氧代-2H-吡喃-3-甲醛 | 88899-61-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 中文名称: 4-甲氧基-6-[(1R,2S,4aR,8aR)-2-甲基-1,2,4a,5,6,7,8,8a-八氢-1-萘基]-2-氧代-2H-吡喃-3-甲醛
• 中文别名: N-[(2,3-二羟基苯基)羰基]-L-丙氨酰-L-苏氨酸
• 英文名称: (+/-)-solanapyrone A
• 英文别名: (+/-)-solanopyrane A；Solanapyrone A；6-[(1R,2S,4aR,8aR)-2-methyl-1,2,4a,5,6,7,8,8a-octahydronaphthalen-1-yl]-4-methoxy-2-oxopyran-3-carbaldehyde
• CAS: 88899-61-0
• 化学式: C₁₈H₂₂O₄
• 分子量: 302.37
• InChiKey: AWQLNKJBXASXDU-SFDCBXKLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-甲氧基-6-[(1R,2S,4aR,8aR)-2-甲基-1,2,4a,5,6,7,8,8a-八氢-1-萘基]-2-氧代-2H-吡喃-3-甲醛 在 四氧化锇 、 对甲苯磺酸 作用下， 以 吡啶 、 苯 为溶剂， 反应 12.0h， 生成 6-((1S,2R,3S,4R,4aS,8aR)-3,4-Dihydroxy-2-methyl-decahydro-naphthalen-1-yl)-3-[1,3]dioxolan-2-yl-4-methoxy-pyran-2-one
  参考文献：
  名称：

  （-）-solanapyrone A的绝对配置

  摘要：

  通过对二苯甲酸酯衍生物应用CD激子手性法，证实了（-）-茄吡喃酮A的绝对构型。

  DOI：

  10.1016/s0040-4039(00)94851-2
• 作为产物：
  描述：

  去氢乙酸 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 sodium periodate 、 四氧化锇 、 水 、 对甲苯磺酰氯 、 thallium(III) nitrate 、 silver(l) oxide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 氯仿 、 水 、 二甲基亚砜 为溶剂， 反应 33.33h， 生成 4-甲氧基-6-[(1R,2S,4aR,8aR)-2-甲基-1,2,4a,5,6,7,8,8a-八氢-1-萘基]-2-氧代-2H-吡喃-3-甲醛
  参考文献：
  名称：

  Synthesis of (±)-solanapyrone A

  摘要：

  DOI：

  10.1016/s0040-4039(00)95319-x

文献信息

• Solanapyrones, Phytotoxins Produced by<i>Alternaria solani</i>: Biosynthesis and Isolation of Minor Components
  作者：Hideaki OIKAWA、Tomohiro YOKOTA、Chiaki SAKANO、Yuichi SUZUKI、Akira NAYA、Akitami ICHIHARA

  DOI：10.1271/bbb.62.2016

  日期：1998.1

  Two minor components of solanapyrones D and E, phytotoxins from Alternaria solani, were isolated. The absolute stereochemistry of D and the optical purity of solanapyrones A and D were determined by chemical transformation and measurement of the CD spectrum. In addition, complete signal assignment of the (1)H- and (13)C-NMR spectra of solanapyrones A and D, and their solution conformations were studied

  solanapyrones D和E的两个次要成分，即来自Alternaria solani的植物毒素被分离出来。D的绝对立体化学和茄吡喃酮A和D的光学纯度通过化学转化和CD光谱的测量来确定。此外，研究了茄吡喃酮A和D的（1）H-和（13）C-NMR谱的完整信号分配，以及它们的溶液构象。各种同位素标记的乙酸盐和蛋氨酸的进料实验建立了茄那隆的生物合成途径。讨论了茄胺酮对生菜幼苗的植物毒性。
• Enzymatic activity catalysing exo-selective Diels–Alder reaction in solanapyrone biosynthesis
  作者：Hideaki Oikawa、Kinya Katayama、Yuichi Suzuki、Akitami Ichihara

  DOI：10.1039/c39950001321

  日期：——

  The crude enzyme from Alternaria solani is able to catalyse the [4 + 2] cycloaddition of prosolanapyrone III 6 to the exo adduct solanapyrone A 1 whose optical purity is estimated as 92 ± 8% e.e. by HPLC analysis monitored using a CD spectrometer; this enzyme also catalyses the oxidation and [4 + 2] cycloaddition of prosolanapyrone II 5 to 1 with 99 ± 4% e.e.

  来自Alternaria solani的粗酶能够催化prosolanapyrone III 6与外加合物solanapyrone A 1的[4 + 2]环加成反应，其光学纯度通过HPLC分析和使用CD光谱仪监测，估计为92 ± 8% e.e.；该酶还能催化prosolanapyrone II 5与1的氧化和[4 + 2]环加成反应，其光学纯度为99 ± 4% e.e.。
• Purification and N-Terminal Amino Acid Sequence of Solanapyrone Synthase, A Natural Diels-Alderase from<i>Alternaria solani</i>
  作者：Kinya KATAYAMA、Tomonori KOBAYASHI、Masao CHIJIMATSU、Akitami ICHIHARA、Hideaki OIKAWA

  DOI：10.1271/bbb.70600

  日期：2008.2.23

  The first natural Diels-Alderase, solanapyrone synthase, was purified 1,630-fold from a crude extract. The 41-kDa protein on SDS-polyacrylamide gel electrophoresis was identified as truncated solanapyrone synthase, and its N-terminal amino acid sequence was found to be QETQNLNNFLESNAINP.

  从天然提取物中纯化出第一种天然Diels-Alderase solanapyrone合酶1,630倍。SDS-聚丙烯酰胺凝胶电泳上的41 kDa蛋白被鉴定为截短的茄那酮合酶，其N端氨基酸序列为QETQNLNNFLESNAINP。
• Solanapyrone Synthase, a Possible Diels-Alderase and Iterative Type I Polyketide Synthase Encoded in a Biosynthetic Gene Cluster from Alternaria solani
  作者：Ken Kasahara、Takanori Miyamoto、Takashi Fujimoto、Hiroki Oguri、Tetsuo Tokiwano、Hideaki Oikawa、Yutaka Ebizuka、Isao Fujii

  DOI：10.1002/cbic.201000173

  日期：——

  Enzyme‐catalyzed Diels–Alder cycloaddition: The biosynthetic gene cluster for solanapyrone has been cloned from Alternaria solani. The polyketide synthase product was identified as desmethylprosolanapyrone I. Expression and in vitro analysis indicated that Sol5—solanapyrone synthase—is a possible enzyme that catalyzes Diels–Alder cycloaddition.

  酶催化的Diels-Alder环加成： solanapyrone的生物合成基因簇已从Alternaria solani中克隆而来。该聚酮化合物合酶产物被鉴定为去甲基普萘拉那酮I。表达和体外分析表明，Sol5（索拉那酮合酶）是可能催化Diels-Alder环加成反应的酶。
• Total Synthesis of (−)-Solanapyrone A via Enzymatic Diels−Alder Reaction of Prosolanapyrone
  作者：Hideaki Oikawa、Tomonori Kobayashi、Kinya Katayama、Yuichi Suzuki、Akitami Ichihara

  DOI：10.1021/jo980743r

  日期：1998.11.1

  The syntheses of prosolanapyrones I (6) and II (7) via the aldol reactions of pyrone and dienal segments have been achieved in five steps in 31% overall yield for 6 and seven steps in 5% overall yield for 7. An improved synthetic route starting from vinylpyrone 27 provided 7 in 11 steps in 12% overall yield. The enzymatic Diels-Alder reaction of 7 affords (-)-solanapyrone A (1) with high enantioselectivity and with good exo-selectivity, which is difficult to attain by chemical methods. In addition, a crude enzyme preparation from Alternaria solani has been used to perform a kinetic resolution of(+/-)-3.