(3aR,4R,7S,7aS)-rel-3a,4,7,7a-四氢-4,7-甲桥异苯并呋喃-1(3H)-酮 | 95340-93-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 中文名称: (3aR,4R,7S,7aS)-rel-3a,4,7,7a-四氢-4,7-甲桥异苯并呋喃-1(3H)-酮
• 中文别名: 3-羟甲基-5-降冰片烯-2-羧酸内酯
• 英文名称: (3aα,4β,7β7aα)-3a,4,7,7a-Tetrahydro-4,7-methanoisobenzofuran-1(3H)-on
• 英文别名: (+/-)-cis-endo-3-(hydroxymethyl)bicyclo<2.2.1>hept-5-ene-2-carboxylic acid lactone；(1SR,2SR,6RS,7RS)-4-oxatricyclo[5.2.1.0^2,6]dec-8-en-3-one；3a,4,7,7a-tetrahydro-4,7-methanoisobenzo-furan-1(3H)-one；cis-exo-3-oxabicyclo[2.2.1]dec-7-en-2-one；(1R,2R,6S,7S)-4-oxatricyclo[5.2.1.02,6]dec-8-en-3-one
• CAS: 95340-93-5
• 化学式: C₉H₁₀O₂
• 分子量: 150.177
• InChiKey: WOJWXGGCIZZKFQ-VGRMVHKJSA-N

物化性质

• 熔点：
  64-65℃
• 沸点：
  301℃
• 密度：
  1.248
• 闪点：
  123℃

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2932209090

反应信息

• 作为反应物：
  描述：

  (3aR,4R,7S,7aS)-rel-3a,4,7,7a-四氢-4,7-甲桥异苯并呋喃-1(3H)-酮 在 palladium 10% on activated carbon 、 氢气 作用下， 以 乙醇 为溶剂， 反应 1.0h， 以92%的产率得到(2R,3S)-cis-endo-3-(hydroxymethyl)bicyclo[2.2.1]heptane-2-carboxylic acid lactone
  参考文献：
  名称：

  Synthesis and Insecticidal Activity of Lactones Derived from Furan-2(5H)-one

  摘要：

  Ten 4,7-methanoisobenzofuran-1(3H)-ones were synthesized and their insecticidal activities against the insect pest Diaphania hyalinata were evaluated. The most active substances have been selected from the initial screening to find the dose to kill 50 (LD50) and 90% (LD90) of the melonworm. Time-mortality curves of the three selected formulations at the LD90 concentration have been made against D. hyalinata. From the time-mortality curves we found that the formulation (3aR,4R,5S,6S,7S,7aS)- and (3aS,4S,5R,6R,7R,7aR)-5,6-dichlorohexahydro-4,7-methanoisobenzofuran-1(3H)-one + (3aR,4R,5R,6R,7S,7aS)- and (3aS,4S,5S,6S,7R,7aR)-5,6-dichlorohexahydro-4,7-methanoisobenzofuran-1(3H)-one has killed 50% of the melonworm after 2 h, presenting the best knockdown effect. Bioassays against Solenopsis saevissima and Tetragonisca angustula were carried out for the lactones selected in the initial screening against D. hyalinata. The formulation (3aS,4R,5S,6S,7S,7aR)- and (3aR,4S,5R,6R,7R,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one + (3aS,4R,5R,6R,7S,7aR)- and (3aR,4S,5S,6S,7R,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one has killed 31.25 and 68.30% of the pest natural enemy and the pollinator bee, respectively. At the same concentration this formulation killed 90% of D. hyalinata. The selectivity in favor of the non-target organisms has rendered this formulation a position as a promising agrochemical.

  DOI：

  10.5935/0103-5053.20150217
• 作为产物：
  描述：

  (1R,2R,6S,7S)-4-oxa-tricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione 在 sodium tetrahydroborate 作用下， 生成 (3aR,4R,7S,7aS)-rel-3a,4,7,7a-四氢-4,7-甲桥异苯并呋喃-1(3H)-酮
  参考文献：
  名称：

  中环酸酐合成 1,3-氨基醇的新方法

  摘要：

  1,3-氨基醇及其衍生物在具有生物活性的各种化合物的合成中起着重要作用。例如，天然存在的氨基糖是几种抗生素的重要成分。2 含有氨基环醇部分的碳环核苷显示出强大的抗病毒活性。~ 手性 1,3-氨基醇可以通过酶促拆分从其外消旋混合物中获得，并且已经被用作不对称合成中的手性助剂。虽然已经描述了几种 1,3-氨基醇的合成方法，但据我们所知，只有 Fulop 和同事报道了从内消旋环酸酐制备 1,3-氨基醇的途径。在 Fulop 的方法中，通过甲酰胺的霍夫曼重排制备巴胺酸，甲酰胺是通过氨解环酐获得的。氢化铝锂 AH) 氨基酸的还原得到 1,3-氨基醇。~~~我们现在报告了从内消旋环酸酐制备 1,3-氨基醇的新途径。用氨处理由容易获得的狄尔斯-阿尔德加合物 1a、b 制备的内酯 2a、b，得到酰氨基醇 3a.b。虽然没有发生酰胺醇 3 与次氯酸钠的霍夫曼重排，但醇 3a 与双（乙酰氧基）碘苯在温和条件下的反应导致

  DOI：

  10.1080/00304940309355856

文献信息

• Desymmetrisation of meso-Anhydrides Utilising (S)-Proline Derivatives
  作者：Thomas Albers、Stefano C.G. Biagini、David E. Hibbs、Michael B. Hursthouse、K. M. Abdul Malik、Michael North、Eugenio Uriarte、Guiseppe Zagotto

  DOI：10.1055/s-1996-4223

  日期：1996.3

  meso-Anhydrides derived from norbornanes and norbornenes, undergo an asymmetric ring opening upon treatment with (S)-proline derivatives, to give amido acids with moderate to excellent enantiomeric excesses. A cyclopropane derived anhydride was also desymmetrised in this way, whilst cyclohexyl derived anhydrides gave a 1:1 mixture of diastereomers. The origin of the desymmetrisation is explained by a model based on steric interactions in the transition state.

  来源于诺出生物烯和诺玻尔烯的中间酐在与(S)-脯氨酸衍生物反应时，会发生不对称环打开，生成具有中等到优异对映体过剩的氨基酸。一种源自环丙烷的酐也以这种方式进行了不对称化，而源自环己烷的酐则生成了1:1的立体异构体混合物。去对称化的来源通过一个基于过渡态的空间相互作用的模型进行了说明。
• Catalytic Enantioselective Desymmetrization of <i>Meso</i> Cyclic Anhydrides via Iridium-Catalyzed Hydrogenation
  作者：Tang-Lin Liu、Wei Li、Huiling Geng、Chun-Jiang Wang、Xumu Zhang

  DOI：10.1021/ol400533g

  日期：2013.4.5

  A novel method to desymmetrize meso-anhydrides into lactones via asymmetric hydrogenation catalyzed by the Ir–C3*-TunePhos complex has been developed. Various chiral lactones were synthesized with full conversion and excellent enantioselectivity under high reaction temperature.

  已开发出一种通过Ir–C 3 * -TunePhos络合物催化的不对称加氢将内消旋酸酐消旋成内酯的新方法。在高反应温度下合成了各种手性内酯，它们具有完全的转化率和优异的对映选择性。
• Broad-Spectrum Enantioselective Diels−Alder Catalysis by Chiral, Cationic Oxazaborolidines
  作者：Do Hyun Ryu、Thomas W. Lee、E. J. Corey

  DOI：10.1021/ja027468h

  日期：2002.8.1

  catalysts for Diels-Alder addition of cyclopentadiene to a wide variety of dienophiles. Adducts have been obtained in excellent yield and enantioselectivity from alpha,beta-unsaturated esters, lactones, and cyclic ketones. The absolute facial selectivity for each of these substrates follows a common pattern which differs from that observed with alpha,beta-enals. The different reaction channels can be

  阳离子手性路易斯酸 1 和 2 由相应的中性恶唑硼烷的三氟甲磺酸质子化产生，可作为环戊二烯与各种亲二烯体的 Diels-Alder 加成反应的优良催化剂。已从 α、β-不饱和酯、内酯和环酮以优异的产率和对映选择性获得加合物。这些基质中每一种的绝对面部选择性遵循一个共同的模式，该模式不同于用 alpha,beta-enals 观察到的模式。可以根据通过复合物 3（对于 α、β-烯醛）和 4（对于 α、β-烯酮和酯）的途径来理解不同的反应通道。
• Dimethylaluminum methide complex Tf2CHAlMe2: an effective catalyst for Diels–Alder reaction of α,β-unsaturated lactone derivatives with cyclopentadiene
  作者：Hikaru Yanai、Arata Takahashi、Takeo Taguchi

  DOI：10.1016/j.tet.2007.09.061

  日期：2007.12

  catalyst system for the catalytic DA reaction of less reactive α,β-unsaturated lactone derivative with cyclopentadiene (CP). In this catalyst system, Tf2CHAlMe2 is an active species and an excess amount of Me3Al plays an important role to lower the catalyst loading. Substituent effect of the lactone framework on π-facial selectivity was also examined. In the reactions of both γ-substituted 5-membered lactone

  发现通过将Tf 2 CH 2和Me 3 Al混合而获得的路易斯酸是反应性较低的α，β-不饱和内酯衍生物与环戊二烯（CP）的催化DA反应的有效催化剂体系。在该催化剂体系中，Tf 2 CHAlMe 2是活性物质，过量的Me 3 Al在降低催化剂负载量方面起着重要作用。还研究了内酯骨架对π面选择性的取代作用。在γ取代的5元内酯衍生物和γ或δ甲基化的6元内酯衍生物与CP的反应中，对抗观察到γ-或δ-取代基的表面。另一方面，在γ-或γ-甲基化的7元内酯衍生物的情况下，CP有利地侵蚀了合成面上。
• Characterization of novel isobenzofuranones by DFT calculations and 2D NMR analysis
  作者：Milena G. Teixeira、Elson S. Alvarenga

  DOI：10.1002/mrc.4411

  日期：2016.8

  7aR)‐5,6‐dibromohexahydro‐4,7‐methanoisobenzofuran‐1(3H)‐one and (3aR,4S,5S,6R,7R,7aS)‐5,6‐dibromohexahydro‐4,7‐methanoisobenzofuran‐1(3H)‐one (5). Following the initial analysis of the NMR spectra and the proposed two novel unforeseen products, we have decided to fully analyze the classical and non‐classical assay structures with the aid of computational calculations. Computation to predict the 13C and

  邻苯二甲酸酯经常存在于天然存在的物质中，并表现出广泛的生物活性。在寻找具有杀虫活性的化合物的过程中，苯酞已被用作合成新型潜在农用化学品的通用构件。在我们的工作中，呋喃-2(5H)-酮和环戊二烯之间的 Diels-Alder 反应被成功地用于获得 (3aR,4S,7R,7aS)-3a,4,7,7a-四氢-4,7-methanoisobenzofuran ‐1(3H)-one 和 (3aS,4R,7S,7aR)-3a,4,7,7a-四氢-4,7-methanoisobenzofuran-1(3H)-one (2) 和 (3aS,4S,7R) ,7aR)-3a,4,7,7a-四氢-4,7-methanoisobenzofuran-1(3H)-one 和 (3aR,4R,7S,7aS)-3a,4,7,7a-四氢-4,7 -methanoisobenzofuran-1(3H)-one (3)。内加合物