(-)-(3aS,7aS)-3-Methylenehexahydrobenzofuran-2(3H)-one | 16822-06-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: (-)-(3aS,7aS)-3-Methylenehexahydrobenzofuran-2(3H)-one
• 英文别名: (-)-(3aS,7aS)-3-methylene-cis-hexahydrobenzofuran-2(3H)-one；(3As,7aS)-3-methylidene-3a,4,5,6,7,7a-hexahydro-1-benzofuran-2-one
• CAS: 16822-06-3
• 化学式: C₉H₁₂O₂
• 分子量: 152.193
• InChiKey: JZULHXPIDKRFAY-YUMQZZPRSA-N

物化性质

• 沸点：
  60 °C
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• 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

反应信息

• 作为反应物：
  描述：

  (-)-(3aS,7aS)-3-Methylenehexahydrobenzofuran-2(3H)-one 、 beta-胸苷 以 丙酮 为溶剂， 以10%的产率得到
  参考文献：
  名称：

  Chronic Actinic Dermatitis to Sesquiterpene Lactones: [2+2] Photoreaction Toward Thymidine of (+) and (−) α-Methylene-Hexahydrobenzofuranone with a cis Ring Junction

  摘要：

  Abstract(+) and (−) α‐methylene‐hexahydrobenzofuranone derivatives with a stereochemically pure cis ring junction were used as models of sesquiterpene lactones to study their photoreactivity toward thymidine. After 313 nm irradiation of a deoxygenated acetone solution of lactone models and thymidine, six [2+2] photoadducts were isolated for each enantiomer and fully characterized by a combination of NMR experiments. A common syn regioselectivity and exo stereoselectivity were observed for photoadducts. This high photoreactivity of α‐methylene‐γ‐butyrolactone ring toward thymidine could be an explanation of the progressive evolution of allergic contact dermatitis toward chronic actinic dermatitis.

  DOI：

  10.1111/j.1751-1097.2009.00691.x
• 作为产物：
  描述：

  (3aR,7aS)-3-Methyl-3-phenylselanyl-hexahydro-benzofuran-2-one 在 双氧水 、 溶剂黄146 作用下， 生成 (-)-(3aS,7aS)-3-Methylenehexahydrobenzofuran-2(3H)-one
  参考文献：
  名称：

  Synthesis and biological resolution of condensed bicyclic isoparaconic acid † derivatives

  摘要：

  通过固定化 Lipozyme® 实现了手性外消旋 (1R*,3aS*,7aS*)-六氢-2-氧代苯并呋喃-3-基乙酸乙酯的动力学拆分。在低转化值下，以 84% ee 分离出 (-)-酸，而在高转化值下，获得了 98% ee 的 (+)-酯。它们的构型是通过将酸转化为已知绝对构型的相应α-亚甲基衍生物来确定的。

  DOI：

  10.1039/b001615m

文献信息

• A Highly Stereoselective Divergent Synthesis of Bicyclic Models of Photoreactive Sesquiterpene Lactones
  作者：Sébastien Fuchs、Valérie Berl、Jean-Pierre Lepoittevin

  DOI：10.1002/ejoc.200600611

  日期：2007.3

  Sesquiterpene lactones are natural stereochemically pure compounds, which show a number of biological activities. In order to study the reactivity of sesquiterpene lactones in biological systems, we describe herein the asymmetric synthesis of a simple model, the α-methylene-hexahydrobenzofuranone 1, which includes the α-methylene-γ-butyrolactone moiety and presents all the different possible ring junctions

  倍半萜内酯是天然立体化学纯化合物，具有多种生物活性。为了研究倍半萜内酯在生物系统中的反应性，我们在此描述了一个简单模型 α-亚甲基-六氢苯并呋喃酮 1 的不对称合成，该模型包括 α-亚甲基-γ-丁内酯部分并呈现所有不同的可能环路口。对映选择性是通过不对称钯催化的烯丙基取代获得的，非对映选择性是通过碘内酯化实现的。该策略提供了对映体过量 >98% 的不同内酯。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• OKADA, YOSHIHARU;MINAMI, TORU;SASAKI, YORITAKA;UMEZU, YASUO;YAMAGUCHI, MA+, TETRAHEDRON LETT., 31,(1990) N7, C. 3905-3908
  作者：OKADA, YOSHIHARU、MINAMI, TORU、SASAKI, YORITAKA、UMEZU, YASUO、YAMAGUCHI, MA+

  DOI：——

  日期：——
• TETRAHYDRONAPHTHO[1,2-B]FURAN-2(3H)-ONE DERIVATIVE AND PREPARATION AND USE THEREOF IN PHARMACEUTICALS
  申请人：Shanghai Qingdong Biotechnology Co., Ltd

  公开号：EP3653614B1

  公开（公告）日：2022-04-20
• Synthesis and biological resolution of condensed bicyclic isoparaconic acid † derivatives
  作者：Sara Drioli、Fulvia Felluga、Cristina Forzato、Giuliana Pitacco、Ennio Valentin

  DOI：10.1039/b001615m

  日期：——

  Kinetic resolution of chiral racemic (1R*,3aS*,7aS*)-hexahydro-2-oxobenzofuran-3-ylacetic acid ethyl ester was achieved by means of immobilized Lipozyme®. At low conversion values, the (−)-acid was isolated with 84% ee, while at high conversion values the (+)-ester was obtained with 98% ee. Their configurations were determined by transformation of the acid into the corresponding α-methylene derivative of known absolute configuration.

  通过固定化 Lipozyme® 实现了手性外消旋 (1R*,3aS*,7aS*)-六氢-2-氧代苯并呋喃-3-基乙酸乙酯的动力学拆分。在低转化值下，以 84% ee 分离出 (-)-酸，而在高转化值下，获得了 98% ee 的 (+)-酯。它们的构型是通过将酸转化为已知绝对构型的相应α-亚甲基衍生物来确定的。
• Chronic Actinic Dermatitis to Sesquiterpene Lactones: [2+2] Photoreaction Toward Thymidine of (+) and (−) α-Methylene-Hexahydrobenzofuranone with a cis Ring Junction
  作者：Sébastien Fuchs、Valérie Berl、Jean-Pierre Lepoittevin

  DOI：10.1111/j.1751-1097.2009.00691.x

  日期：——

  Abstract(+) and (−) α‐methylene‐hexahydrobenzofuranone derivatives with a stereochemically pure cis ring junction were used as models of sesquiterpene lactones to study their photoreactivity toward thymidine. After 313 nm irradiation of a deoxygenated acetone solution of lactone models and thymidine, six [2+2] photoadducts were isolated for each enantiomer and fully characterized by a combination of NMR experiments. A common syn regioselectivity and exo stereoselectivity were observed for photoadducts. This high photoreactivity of α‐methylene‐γ‐butyrolactone ring toward thymidine could be an explanation of the progressive evolution of allergic contact dermatitis toward chronic actinic dermatitis.