(2S,3R)-2-phenyl-3-methoxycarbonyl-2,3-dihydrobenzofuran | 737766-28-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 2-芳基苯并呋喃类黄酮
• 英文名称: (2S,3R)-2-phenyl-3-methoxycarbonyl-2,3-dihydrobenzofuran
• 英文别名: methyl (2S,3R)-2-phenyl-2,3-dihydro-1-benzofuran-3-carboxylate
• CAS: 737766-28-8
• 化学式: C₁₆H₁₄O₃
• 分子量: 254.285
• InChiKey: BXCMWUUBPKZMDL-HUUCEWRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3R)-2-phenyl-3-methoxycarbonyl-2,3-dihydrobenzofuran 在 sodium hydroxide 作用下， 反应 5.5h， 以70%的产率得到
  参考文献：
  名称：

  Khanna, Mahavir S., Organic Preparations and Procedures International, 1994, vol. 26, # 1, p. 125 - 127

  摘要：

  DOI：
• 作为产物：
  描述：

  2-(苯基甲氧基)-苯乙酸甲酯 在 dirhodium(II) tetrakis[(S)-N-phthaloyl-tert-leucinate] p-acetamidebenzenesulfonyl azide 、 1,8-diazabicylo-7-undecene 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 25.0h， 生成 (2S,3R)-2-phenyl-3-methoxycarbonyl-2,3-dihydrobenzofuran
  参考文献：
  名称：

  Enantio- and Diastereoselective Synthesis of cis-2-Aryl-3-methoxycarbonyl-2,3-dihydrobenzofurans via the Rh(II)-Catalyzed C−H Insertion Process

  摘要：

  [GRAPHICS]The enantioselective intramolecular C-H insertion reaction of aryldiazoacetates has been explored with use of dirhodium(II) carboxylate catalysts, which incorporate N-phthaloyl- or N-benzene-fused-phthaloyl-(S)-amino acids as chiral bridging ligands. Dirhodium tetrakis[N-phthaloyl-(S)tert-leucinate], Rh-2(S-PTTL)(4), has proven to be the catalyst of choice for this process, providing exclusively cis-2-aryl-3-methoxycarbonyl-2,3-dihydobenzofurans in up to 94% ee.

  DOI：

  10.1021/ol0267127

文献信息

• Catalysts for use in enantioselective synthesis
  申请人：The Research Foundation of State University of New York

  公开号：US07385064B1

  公开（公告）日：2008-06-10

  Disclosed are compounds having the following formula: in which Z11 is selected from a substituted or unsubstituted saturated adamantyl or other polycyclic group and a substituted or unsubstituted branched acyclic group containing at least 5 carbon atoms at least one of which is a tertiary carbon; and in which Z12 is a cyclic imide. Methods of using these compounds as chiral catalysts for carbenoid reactions and for enantioselective C—H aminations are also described.

  揭示了具有以下结构的化合物： 其中Z11选自取代或未取代的饱和脂肪基或其他多环基团以及取代或未取代的支链无环基团，其中至少含有5个碳原子，其中至少一个是三级碳；Z12为环酰亚胺。还描述了将这些化合物用作手性催化剂进行卡宾反应和对映选择性C—H胺化的方法。
• A New Chiral Rh(II) Catalyst for Enantioselective [2 + 1]-Cycloaddition. Mechanistic Implications and Applications
  作者：Yan Lou、Manabu Horikawa、Robin A. Kloster、Natalie A. Hawryluk、E. J. Corey

  DOI：10.1021/ja047064k

  日期：2004.7.1

  A novel chiral Rh(II) catalyst (1) is introduced for the [2 + 1]-cycloaddition of ethyl diazoacetate to terminal acetylenes and olefins with high enantioselectivity. The catalyst 1 consists of one acetate bridging group and three mono-N-triflyldiphenylimidazoline-2-one bidentate ligands (DPTI) spanning the Rh(II)-Rh(II) metallic center in a structure that was determined by single-crystal X-ray diffraction

  引入了一种新型手性 Rh(II) 催化剂 (1)，用于以高对映选择性将重氮乙酸乙酯 [2 + 1]-环加成到末端乙炔和烯烃。催化剂 1 由一个乙酸酯桥接基团和三个单-N-三氟甲基二苯基咪唑啉-2-一二齿配体（DPTI）组成，该配体跨越 Rh(II)-Rh(II) 金属中心，结构由单晶 X-射线衍射分析。提出了一种合理的机制，为 [2 + 1]-环加成反应的对映选择性和绝对立体化学过程提供了直接的解释。这种解释的一个关键因素是中间Rh-卡宾配合物中桥接乙酸酯基团的Rh-O键之一断裂，形成新的五配位Rh卡宾配合物（形式为1。5价Rh)，可以与炔属或烯烃底物的CC π-键发生[2 + 2]-环加成。所得加合物的还原消除提供环丙烯或环丙烷产物。与桥接乙酸酯正交的两个 DPTI 配体的 C2 对称性也有助于观察到的高对映选择性和机械清晰度。催化剂 1 在 0.5 mol% 时有效发挥作用，可有效回收
• A Concise Route to Dihydrobenzo[<i>b</i>]furans: Formal Total Synthesis of (+)-Lithospermic Acid
  作者：Joshua Fischer、G. Paul Savage、Mark J. Coster

  DOI：10.1021/ol201130h

  日期：2011.7.1

  benzofuran reduction (Mg, MeOH, NH4Cl) provides a convergent and modular synthetic route to trans-2-aryl-2,3-dihydrobenzo[b]furan-3-carboxylates, which are a structural feature of numerous biologically active natural products. This versatile strategy was applied to the formal total synthesis of the anti-HIV natural product (+)-lithospermic acid.

  Sonogashira偶联，Pd（II）催化的羰基环化和苯并呋喃还原（Mg，MeOH，NH 4 Cl）的序列为反式-2-芳基-2,3-二氢苯并[ b ]呋喃提供了一种收敛的模块化合成途径。-3-羧酸盐，是许多具有生物活性的天然产物的结构特征。这种多用途的策略适用于抗HIV天然产物（+）-紫精酸的正式全合成。
• Dirhodium Carboxylate Catalysts from 2‐Fenchyloxy or 2‐Menthyloxy Arylacetic Acids: Enantioselective C−H Insertion, Aromatic Addition and Oxonium Ylide Formation/Rearrangement
  作者：Aoife M. Buckley、Daniel C. Crowley、Thomas A. Brouder、Alan Ford、U. B. Rao Khandavilli、Simon E. Lawrence、Anita R. Maguire

  DOI：10.1002/cctc.202100924

  日期：2021.10.19

  A new class of rhodium carboxylate complexes, which contain phenylacetate ligands substituted with bulky chiral alkoxy substituents, has been prepared, and the application of these complexes in some representative carbene transfer processes of α-diazocarbonyl compounds is described. Good enantioselectivity is obtained across a range of transformations.

  制备了一类新的羧酸铑配合物，其中含有被大手性烷氧基取代基取代的苯乙酸配体，并描述了这些配合物在α-重氮羰基化合物的一些代表性卡宾转移过程中的应用。通过一系列的转化可以获得良好的对映选择性。
• Universal Strategy for the Immobilization of Chiral Dirhodium Catalysts
  作者：Huw M. L. Davies、Abbas M. Walji

  DOI：10.1021/ol0508835

  日期：2005.7.1

  [reaction: see text] Chiral rhodium(II) catalysts used in asymmetric carbenoid chemistry can be efficiently heterogenized using a novel immobilization strategy. The immobilized catalysts display similar reactivity and stereoselectivity to their homogeneous counterparts and can be effectively recycled with limited loss in stereoselectivity.

  [反应：参见正文]使用新型固定化策略可以有效地异质化不对称类胡萝卜素化学中使用的手性铑（II）催化剂。固定化催化剂显示出与其均相同类催化剂相似的反应性和立体选择性，并且可以有效地循环利用，而立体选择性的损失有限。