methyl 2-diazo-2-(2-((4-methoxybenzyl)oxy)phenyl)acetate | 478157-01-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: methyl 2-diazo-2-(2-((4-methoxybenzyl)oxy)phenyl)acetate
• 英文别名: Methyl 2-diazo-2-[2-[(4-methoxyphenyl)methoxy]phenyl]acetate；methyl 2-diazo-2-[2-[(4-methoxyphenyl)methoxy]phenyl]acetate
• CAS: 478157-01-6
• 化学式: C₁₇H₁₆N₂O₄
• 分子量: 312.325
• InChiKey: HXPZRFPRPAMJSO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  46.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2-diazo-2-(2-((4-methoxybenzyl)oxy)phenyl)acetate 在 dirhodium(II) tetrakis sodium methylate 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 反应 1.5h， 生成 (2R,3R)-2,3-trans-3-methoxycarbonyl-2-(4-methoxyphenyl)-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
• 作为产物：
  描述：

  2-羟基苯乙酸甲酯 在 4-乙酰氨基苯磺酰叠氮 、 potassium carbonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 sodium iodide 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 生成 methyl 2-diazo-2-(2-((4-methoxybenzyl)oxy)phenyl)acetate
  参考文献：
  名称：

  无金属串联重排/内酯化：获得3,3-二取代的苯并呋喃-2-（3H）-酮

  摘要：

  通过α-芳基-α-重氮乙酸酯与三芳基硼烷的反应，提出了一种新颖的无金属合成3,3-二取代的苯并呋喃-2-（3 H）-酮的方法。最初，已经成功地研究了三芳基硼烷在α-重氮乙酸酯的α-芳基化中的作用，但是在邻位存在杂原子的情况下，烯醇硼中间体发生分子内重排以形成季中心。该中间体环化以良好的收率提供有价值的3,3-二取代的苯并呋喃酮。

  DOI：

  10.1002/anie.201902985

文献信息

• Tandem Oxidation/Cyclization Reaction of 4-(Arylmethyl)oxy-2-diazobutyrate Derivatives
  作者：Seiichi Nakamura、Hideaki Kondo、Shuji Nagano、Hiroyuki Yamakoshi

  DOI：10.3987/com-18-s(t)67

  日期：——

  A tandem oxidation/cyclization reaction of gamma-(arylmethyl)oxy-alpha-diazobutyrate derivatives was investigated. While oxidative cleavage of the PMB ether was only observed upon treatment of an alpha-diazo-beta-ketoester with DDQ, oxidation of alpha-diazo esters with an sp(3) carbon at the beta-position was accompanied by intramolecular attack of the diazo carbon atom and expulsion of the nitrogen gas to give 2,3-dihydrofurans in modest to good yields when an electron-withdrawing group was substituted at the beta-position. Substrates bearing no electron-withdrawing beta-substituent were found to give rearranged products, albeit in modest yields. A benzofuran derivative could also be obtained, although a hydroquinone adduct was formed as a byproduct.
• Metal‐Free Tandem Rearrangement/Lactonization: Access to 3,3‐Disubstituted Benzofuran‐2‐(3 <i>H</i> )‐ones
  作者：Micol Santi、Darren M. C. Ould、Jan Wenz、Yashar Soltani、Rebecca L. Melen、Thomas Wirth

  DOI：10.1002/anie.201902985

  日期：2019.6.3

  A novel metal‐free synthesis of 3,3‐disubstituted benzofuran‐2‐(3H)‐ones through reacting α‐aryl‐α‐diazoacetates with triarylboranes is presented. Initially, triarylboranes were successfully investigated in α‐arylations of α‐diazoacetates, however in the presence of a heteroatom in the ortho position, the boron enolate intermediate undergoes an intramolecular rearrangement to form a quaternary center

  通过α-芳基-α-重氮乙酸酯与三芳基硼烷的反应，提出了一种新颖的无金属合成3,3-二取代的苯并呋喃-2-（3 H）-酮的方法。最初，已经成功地研究了三芳基硼烷在α-重氮乙酸酯的α-芳基化中的作用，但是在邻位存在杂原子的情况下，烯醇硼中间体发生分子内重排以形成季中心。该中间体环化以良好的收率提供有价值的3,3-二取代的苯并呋喃酮。
• Enantio- and Diastereoselective Synthesis of <i>cis</i>-2-Aryl-3-methoxycarbonyl-2,3-dihydrobenzofurans via the Rh(II)-Catalyzed C−H Insertion Process
  作者：Hiroaki Saito、Hiroyuki Oishi、Shinji Kitagaki、Seiichi Nakamura、Masahiro Anada、Shunichi Hashimoto

  DOI：10.1021/ol0267127

  日期：2002.10.1

  [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.