3,4-dihydro-3-(1,1-dimethylethyl)-1H-2-benzopyran-1-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 3,4-dihydro-3-(1,1-dimethylethyl)-1H-2-benzopyran-1-one
• 英文别名: 3-tert-butylisochroman-1-one；3-Tert-butyl-3,4-dihydroisochromen-1-one
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: WYKRFAWMEIQHOO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,3-二氢异苯并呋喃 在 potassium permanganate 、 萘 、 lithium 作用下， 以 水 为溶剂， 反应 27.0h， 生成 3,4-dihydro-3-(1,1-dimethylethyl)-1H-2-benzopyran-1-one
  参考文献：
  名称：

  邻苯二酚的还原亲电取代和扩环成异色满衍生物

  摘要：

  在催化量的萘的存在下，邻苯二甲酸1a与锂金属的还原裂解导致形成稳定的芳族二锂化合物。后者与CO 2，醛或酮的加成物闭环成异色满衍生物，导致原始杂环的扩环。还原亲电取代程序已成功地扩展到取代的酞菁1b和1c，以令人满意的产率提供了相应的异色满-3one。

  DOI：

  10.1016/0040-4039(95)01692-b

文献信息

• Synthesis and application of benzyl-TMS derivatives as bench stable benzyl anion equivalents
  作者：Manas Das、Donal F. O'Shea

  DOI：10.1016/j.tet.2013.05.078

  日期：2013.8

  derivatives are bench stable reagents yet can serve as benzyl anion equivalents under mild reaction conditions. Following activation with fluoride they can successfully participate in a wide range of additions to both non-enolizable and enolizable carbonyls. In addition, their use in the synthesis of isochromanones and trifluoromethylated amines is illustrated. The broad synthetic scope and mild practical

  使用丁基锂/ KO甲苯的区域选择性金属化苄吨BU / TMP（H）（LINK金属化条件），并且随后转移金属化于Si通过与反应的TMSCl为取代benzyltrimethylsilanes的合成的一般单罐方法。ArCH 2 Si（Me）3衍生物是实验室稳定的试剂，但可以在温和的反应条件下用作苄基阴离子当量。用氟化物活化后，它们可以成功地参与不可烯醇化和可烯醇化羰基的多种加成。另外，还说明了它们在异色酮和三氟甲基化胺的合成中的用途。ArCH 2 Si（Me）3的广泛合成范围和温和的实际使用条件 试剂证明了其作为苄基阴离子当量的一般潜力。
• 3,4-Dihydroisocoumarins from α-Bromo-o-tolunitrile and Ketones or Aldehydes
  作者：Takahiro Kanda、Shinzi Kato、Takushi Sugino、Nobuaki Kambe、Akiya Ogawa、Noboru Sonoda

  DOI：10.1055/s-1995-4065

  日期：1995.9

  o-Cyanobenzyllithium (3) was efficiently generated by lithium-tellurium exchange of the corresponding benzylic telluride 2 prepared in situ from lithium butanetellurolate and α-bromo-o-tolunitrile (1). Reaction of ketones or aldehydes with 3 afford substituted 2-hydroxyethylbenzonitriles 4 in high yields. The subsequent acid-catalyzed lactonization gave 3-substituted 3,4-dihydroisocoumarins 5 in good yields. All these successive reactions could be performed in the same reaction flask without isolation of intermediates.

  通过锂碲交换反应，从丁基碲醇锂和α-溴邻甲苯腈（1）原位合成的苄位碲化物（2）高效生成了邻氰苄基锂（3）。酮或醛与（3）反应，以高产率得到取代的2-羟基乙基苯甲腈（4）。随后的酸催化内酯化反应以良好产率得到3-取代的3,4-二氢异香豆素（5）。所有这些连续反应都可以在同一个反应瓶中进行，无需分离中间体。
• Reductive electrophilic substitution of phthalans and ring expansion to isochroman derivatives
  作者：Ugo Azzena、Salvatore Demartis、Maria Giovanna Fiori、Giovanni Melloni、Luisa Pisano

  DOI：10.1016/0040-4039(95)01692-b

  日期：1995.10

  of a stable aromatic dilithium compound. The adducts of the latter with CO2, aldehydes or ketones undergo ring closure to isochroman derivatives, leading to ring expansion of the original heterocycle. The reductive electrophilic substitution procedure was successfully extended to the substituted phthalans 1b and 1c, to afford the corresponding isochroman-3ones in satisfactory yields.

  在催化量的萘的存在下，邻苯二甲酸1a与锂金属的还原裂解导致形成稳定的芳族二锂化合物。后者与CO 2，醛或酮的加成物闭环成异色满衍生物，导致原始杂环的扩环。还原亲电取代程序已成功地扩展到取代的酞菁1b和1c，以令人满意的产率提供了相应的异色满-3one。
• Chromium/Photoredox Dual Catalyzed Synthesis of <i>α</i> ‐Benzylic Alcohols, Isochromanones, 1,2‐Oxy Alcohols and 1,2‐Thio Alcohols
  作者：Subhabrata Dutta、Johannes E. Erchinger、Felix Schäfers、Ankita Das、Constantin G. Daniliuc、Frank Glorius

  DOI：10.1002/anie.202212136

  日期：2022.12.5

  The synthesis of α-benzylic alcohols, functionalized isochromanones, 1,2-oxy alcohols and 1,2-thio alcohols has been successfully achieved by employing a dual catalytic method combining chromium chemistry and photoredox catalysis. This presents a methodology under mild conditions with high functional group tolerance.

  通过采用结合铬化学和光氧化还原催化的双重催化方法，成功合成了α-苄醇、官能化异色满酮、1,2-羟基醇和 1,2-硫醇。这提出了一种在温和条件下具有高官能团耐受性的方法。
• Electron-Transfer-Induced Reductive Cleavage of Phthalans:  Reactivity and Synthetic Applications
  作者：Ugo Azzena、Salvatore Demartis、Giovanni Melloni

  DOI：10.1021/jo9604548

  日期：1996.1.1

  The behavior of phthalan (1a) was investigated under conditions of electron transfer from alkali metals in aprotic solvents. Reaction with lithium in the presence of a catalytic amount of naphthalene in THF led to the reductive cleavage of an arylmethyl carbon-oxygen bond, with formation of a stable dilithium compound. Trapping of this intermediate with several electrophiles (alkyl halides, carbonyl derivatives, CO2) was successful. The extension of this procedure to several substituted phthalans (1b-i) was investigated, and the regiochemistry as well as the synthetic usefulness of these reactions are discussed.