cis-3-hydroxyflavanone

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 黄酮类化合物
• 英文名称: cis-3-hydroxyflavanone
• 英文别名: (2R,3S)-3-hydroxy-2-phenyl-2,3-dihydrochromen-4-one
• 化学式: C₁₅H₁₂O₃
• 分子量: 240.258
• InChiKey: YEDFEBOUHSBQBT-HUUCEWRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  cis-3-hydroxyflavanone 在 盐酸 作用下， 以 丙酮 为溶剂， 反应 0.25h， 以0.21 g的产率得到rac-trans-3-hydroxy-2-phenyl-3,4-dihydro-2H-chromen-4-one
  参考文献：
  名称：

  Hypervalent iodine oxidation of flavanone. Synthesis of cis- and trans-3-hydroxyflavanones

  摘要：

  DOI：

  10.1021/jo00202a001
• 作为产物：
  描述：

  (2E)-1-(2-羟基苯基)-3-苯基-2-丙烯-1-酮 在 盐酸 、 二甲基二环氧乙烷 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙醇 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 3.03h， 生成 cis-3-hydroxyflavanone
  参考文献：
  名称：

  Synthesis and Cyclization of 1-(2-Hydroxyphenyl)-2-propen-1-one Epoxides:  3-Hydroxychromanones and -flavanones versus 2-(1-Hydroxyalkyl)-3-coumaranones

  摘要：

  Competitive alpha and beta cyclization of 2'-hydroxychalcone epoxides affords 2-(alpha-hydroxybenzyl)-3-coumaranone and/or 3-hydroxyflavanones, which depends on the conditions employed. Epoxidation of 2'-hydroxychalcones by dimethyldioxirane followed by either base- or acid-catalyzed ring closure provides a novel, general, and efficient method for the synthesis of trans-3-hydroxyflavanones, which includes also the naturally occurring derivatives. Extension of this two-step procedure to 1-(2-hydroxyphenyl)-2-alken-1-ones was also accomplished. A strong preference for alpha cyclization was observed in the case of beta-unsubstituted or -monoalkylated alpha,beta-enones, while both 2,2-dimethyl-3-hydroxychromanones and 2-(1-hydroxy-1-methylethyl)-3-coumaranones were obtained from the beta,beta-dimethylated substrates.

  DOI：

  10.1021/jo960163z

文献信息

• Oxidative Rearrangement of Flavanones with Thallium(III) Nitrate, Lead Tetraacetate and Hypervalent Iodines in Trimethyl Orthoformate and Perchloric or Sulfuric Acid
  作者：István Németh、Attila Kiss-Szikszai、Tünde Zita Illyés、Attila Mándi、István Komáromi、Tibor Kurtán、Sándor Antus

  DOI：10.5560/znb.2012-0214

  日期：2012.12.1

  flavanone [(±)-1] with thallium(III) nitrate, lead tetracetate, phenyliodonium diacetate (PIDA) or [hydroxyl( tosyloxy)iodo]benzene in trimethyl orthoformate. Besides the major ring-contraction product, the 2,3-dihydrobenzo[b]furan derivative (±)-4a, minor components were also identified, and their structures including the relative stereochemistry and a plausible mechanism of formation are reported and compared

  已经开发了一种 HPLC 监测方案来跟踪黄烷酮 [(±)-1] 与硝酸铊 (III)、四乙酸铅、二乙酸苯基碘 (PIDA) 或 [羟基（甲苯磺酰氧基）碘]苯在原甲酸三甲酯中的反应。除了主要的缩环产物，2,3-二氢苯并[b]呋喃衍生物（±）-4a，还确定了少量组分，并报告了它们的结构，包括相对立体化学和可能的形成机制，并与文献进行了比较数据。通过HPLC在不同条件下监测氧化反应，并测定和比较产物的结构和比例。通过 PIDA 从 (±)-黄烷酮 (1) 形成黄酮 (5) 的优选通过对该试剂添加到 (±)-1 的烯醇醚衍生物形成的中间体的量子化学计算来解释。图解摘要黄烷酮与硝酸铊 (III)、四乙酸铅和高价碘在原甲酸三甲酯和高氯酸或硫酸中的氧化重排
• Synthesis of Racemic and Enantiomerically Enriched a-Oxyfunctionalized Benzocyclanones and Chromanones by Dimethyldioxirane and Dimethyldioxirane/Mn(III) salen System
  作者：Tam�s Patonay、J�zsef Jek�、Attila Kiss-Szikszai、Albert L�vai

  DOI：10.1007/s00706-004-0159-9

  日期：2004.6.1

  Enolacetates of benzocyclanones and chromanones were synthesized and treated with dimethyldioxirane and the asymmetric oxidizing system dimethyldioxirane/chiral, non-racemic Mn(III) salen complex/axial ligand. The latter reagent resulted in the corresponding enantiomerically enriched cyclic alpha-hydroxy ketones and their acetates in moderate-to-good yields and modest enantioselectivity under mild and neutral conditions from tetralone and chromanone. On the contrary, flavanone provided poor yields due to the competitive C-H insertion at position 2. The use of R,R-Mn(III)salen catalyst induced an S absolute configuration at the position alpha in the whole series.
• Dimethyldioxirane Oxidation of Titanium Enolates: Diastereoselective .alpha.-Hydroxylations
  作者：Waldemar Adam、Michael Mueller、Frank Prechtl

  DOI：10.1021/jo00088a015

  日期：1994.5

  The oxidation of titanium enolates, derived from a transmetalation reaction of the corresponding lithium enolates with (i-PrO)(3)TiCl, (Et(2)N)(3)TiCl, or Cp(2)TiCl(2), by dimethyldioxirane has been investigated. Furthermore, the diastereoselective hydroxylation of the chiral metal enolates, e.g., derived from camphor (1f), menthone (1g), flavanone (1h), and 2-benzylcyclopentanone (1i), by dimethyldioxirane has been examined. The diastereoselectivity of the oxygen transfer strongly depends on the metal partner coordinated to the enolate. The titanium enolates 4 resulted in much higher diastereoselectivities (up to 96% de) than the corresponding sodium enolates 5 and at least as high if not higher than the silyl enol ethers 6. Moreover, the aldol reaction of ester-derived sodium enolates with acetone, the unavoidable medium for dimethyldioxirane, could be totally suppressed by the use of the chlorotitanocene enolates 4. Thus, the oxidation of chiral titanium enolates by dimethyldioxirane represents a general, convenient, effective, and chemo- and diastereoselective synthesis of alpha-hydroxy carbonyl compounds.
• A convenient and general synthesis of trans-3-hydroxyflavanones from chalcones by dimethyldioxirane epoxidation and subsequent base-catalyzed cyclization
  作者：Tamás Patonay、Gábor Tóth、Waldemar Adam

  DOI：10.1016/s0040-4039(00)60674-3

  日期：1993.8

  2'-Hydroxychalcone epoxides were found to give trans-3-hydroxyflavanone and 2-(alpha-hydroxybenzyl)-3-coumaranone under basic conditions. Epoxidation of 2'-hydroxychalcones with dimethyldioxirane followed by treatment of tetrabutylammonium hydroxide provides a convenient and general method for the synthesis of trans-3-hydroxyflavanones.