dimethyl 2-((S)-2-((S)-hydroxy(4-bromophenyl)methyl)but-3-en-1-yl)malonate | 1346159-07-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dimethyl 2-((S)-2-((S)-hydroxy(4-bromophenyl)methyl)but-3-en-1-yl)malonate
• CAS: 1346159-07-6
• 化学式: C₁₆H₁₉BrO₅
• 分子量: 371.228
• InChiKey: YWZVGMBHZNHLEC-YGRLFVJLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.64
• 重原子数：
  22.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  72.83
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  2-乙烯基环丙烷-1,1-二羧酸二甲酯 、 对溴苯甲醛 在 potassium phosphate 、 (R)-Ir-SEGPHOS 作用下， 以 四氢呋喃 、 水 、 异丙醇 为溶剂， 反应 24.0h， 生成 dimethyl 2-((S)-2-((S)-hydroxy(4-bromophenyl)methyl)but-3-en-1-yl)malonate 、 dimethyl 2-(2-(hydroxy(4-bromophenyl)methyl)but-3-en-1-yl)malonate
  参考文献：
  名称：

  Polarity Inversion of Donor–Acceptor Cyclopropanes: Disubstituted δ-Lactones via Enantioselective Iridium Catalysis

  摘要：

  The coupling of carbonyl electrophiles at the donor position of donor acceptor cyclopropanes is described, representing an inversion of polarity with respect to conventional reactivity modes displayed by these reagents. Specifically, upon exposure of donor-acceptor cyclopropanes to alcohols in the presence of a cyclometalated iridium catalyst modified by (S)-BINAP, catalytic C-C coupling occurs, providing enantiomerically enriched products of carbonyl allylation. Identical products are obtained upon isopropanol-mediated transfer hydrogenation of donor acceptor cyclopropanes in the presence of aldehydes. The reaction products are directly transformed to cis-4, 5-disubstituted delta-lactones.

  DOI：

  10.1021/ja2090993

文献信息

• Organophosphorus-Catalyzed Borylative Ring-Opening of Vinylcyclopropanes: A Stereoselective Route to δ-Valerolactones
  作者：Krishna Biswas、Aankhi Khamrai、Subrata Malik、Venkataraman Ganesh

  DOI：10.1021/acs.orglett.2c04284

  日期：2023.3.24

  through an organophosphorus-catalyzed borylative ring-opening/allylation of vinylcyclopropanes providing δ-hydroxy esters stereoselectively. The δ-hydroxy esters were lactonized to obtain densely substituted δ-valerolactones. The present methodology exhibited enhanced functional group tolerance compared to the existing metal-mediated methods. A plausible mechanism for borylative ring-opening reaction

  我们通过有机磷催化的乙烯基环丙烷的硼基化开环/烯丙基化立体选择性地提供 δ-羟基酯，报告了一种操作简单的 δ-戊内酯途径。δ-羟基酯被内酯化以获得密集取代的δ-戊内酯。与现有的金属介导方法相比，本方法表现出增强的官能团耐受性。已经提出了一种可能的硼酸化开环反应机制。31 P NMR 研究表明磷鎓两性离子种类的参与。证明了中间体硼酸烯丙酯的合成效用。