prosolanapyrone II | 154584-31-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: prosolanapyrone II
• 英文别名: prosolanapyrome II；3-(hydroxymethyl)-4-methoxy-6-[(1E,7E,9E)-undeca-1,7,9-trienyl]pyran-2-one
• CAS: 154584-31-3
• 化学式: C₁₈H₂₄O₄
• 分子量: 304.386
• InChiKey: FAKIZFXTXMMNRM-JHHIBIJLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  22
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  prosolanapyrone II 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以63%的产率得到prosolanapyrone III
  参考文献：
  名称：

  Total Synthesis of (−)-Solanapyrone A via Enzymatic Diels−Alder Reaction of Prosolanapyrone

  摘要：

  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.

  DOI：

  10.1021/jo980743r
• 作为产物：
  描述：

  4-甲氧基-6-甲基-2H-吡喃酮 在 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 四丁基氟化铵 、 四氯化钛 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 对甲苯磺酰氯 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 11.0h， 生成 prosolanapyrone II
  参考文献：
  名称：

  Total Synthesis of (−)-Solanapyrone A via Enzymatic Diels−Alder Reaction of Prosolanapyrone

  摘要：

  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.

  DOI：

  10.1021/jo980743r

文献信息

• 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。
• Enzymatic activity and partial purification of solanapyrone synthase: first enzyme catalyzing Diels–Alder reaction
  作者：Kinya Katayama、Tomonori Kobayashi、Hideaki Oikawa、Mamoru Honma、Akitami Ichihara

  DOI：10.1016/s0167-4838(98)00040-5

  日期：1998.5

  In cell-foe extracts of Alternaria solani, an enzymatic activity converting prosolanapyrone II to solanapyrones A and D via oxidation and subsequent Diels-Alder reaction has been found. Chromatography with DEAE-Sepharose provided two active fractions, pools 1 and 2. The former fraction converted prosolanapyrone II to solanapyrones A and D in a ratio of 2.2:1 with optical purities of 99% and 45% ee, respectively. The latter fraction did so in a ratio of 7.6:1 with 99% and nearly 0% ee, respectively. The enzyme partially purified from pool 2 native molecular weight of 40-62 kD and a pi of 4.25. The high reactivity of prosolanapyrone III in aqueous solution and the chromatographic behavior of the enzyme in pool 2 suggest that a single enzyme catalyzes both the oxidation and Diels-Alder reaction. (C) 1998 Elsevier Science B.V. All rights reserved.
• 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.