trans-3-methylene-4,5-diphenyltetrahydrofuran-2-one

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: trans-3-methylene-4,5-diphenyltetrahydrofuran-2-one
• 英文别名: 3-methylene-4,5-trans-diphenyldihydrofuran-2(3H)-one；trans-3-methylene-4,5-diphenyldihydrofuran-2(3H)-one；trans-β,γ-diphenyl-α-methylene-γ-butyrolactone；(4S,5S)-3-methylidene-4,5-diphenyloxolan-2-one
• 化学式: C₁₇H₁₄O₂
• 分子量: 250.297
• InChiKey: VLJQNNIXUWORNH-HZPDHXFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-3-methylene-4,5-diphenyltetrahydrofuran-2-one 以 乙醚 为溶剂， 反应 0.5h， 生成 (E)-but-2-enedioic acid;(3S,4S,5R)-3-[(dimethylamino)methyl]-4,5-diphenyloxolan-2-one
  参考文献：
  名称：

  Synthetic α-(aminomethyl)-γ-butyrolactones and their anti-pancreatic cancer activities

  摘要：

  Aminated alpha-methylene-c-butyrolactones, which are readily synthesized with facile control of the diastereoisomerism, provide an economical and commercially-viable alternative to the use of aminated natural products. These aminoloactones, which exhibit excellent activity against three pancreatic cancer cell lines when measured at 10 mu M-Panc-1, MIA PaCa-2, and BxPC-3-and are comparable to or better than parthenolide and dimethylaminoparthenolide (DMAPT, LC-1). It has also been shown that there is an effect on the biological activity depending on the identity of the amine. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2013.09.065
• 作为产物：
  描述：

  3-hydroxy-2-methylene-4,4-diphenylbutyric acid 在 二氯乙基铝 、 sodium carbonate 作用下， 以 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 0.83h， 生成 trans-3-methylene-4,5-diphenyltetrahydrofuran-2-one
  参考文献：
  名称：

  应变驱动的各向异性重排：α-亚甲基-γ-丁内酯的统一环扩环方法

  摘要：

  已经实现了前所未有的应变驱动的α-亚甲基-β-内酯的重整排列，这使得能够有效利用显示出显着结构多样性的各种α-亚甲基-γ-丁内酯。该反应的几个吸引人的特征，包括出色的效率，高立体特异性，可预测的化学选择性和广泛的底物范围，使其成为合成天然或合成来源的含MBL分子的有力工具。实验和计算证据均表明，致各向异性重排的新变体以二元模式进行：虽然异步协同机制最有可能解释了以氢迁移为特征的反应，但在芳基迁移的情况下，涉及involving离子中间体的逐步过程是有利的。

  DOI：

  10.1002/anie.202013169

文献信息

• Control of Stereochemistry:  A General Synthesis of <i>cis</i>- or <i>trans</i>-β,γ-Disubstituted-γ-butyrolactones Following <i>Z</i>-Crotylboration
  作者：P. Veeraraghavan Ramachandran、Debarshi Pratihar、Debanjan Biswas

  DOI：10.1021/ol061566g

  日期：2006.8.1

  [reaction; see text] A general and practical procedure for the highly diastereoselective preparation of either the cis- or trans-beta,gamma-disubstituted-gamma-butyrolactones by appropriate choice of Lewis or Bronsted acid catalysts during crotylboration or lactonization is reported. The cis-stereochemistry of the Z-crotylboration product can be inverted with strong acids during lactonization. A carbocation

  [反应; 见文]为顺式或反式-β-的高度非对映制备的一般和实用程序，则报告crotylboration或内酯化过程中的γ-二取代-γ丁内酯由路易斯或布朗斯台德酸催化剂的合适的选择。Z-巴豆基硼化产物的顺式立体化学可以在内酯化过程中用强酸逆转。已经提出了碳正离子化机理和催化循环。
• An efficient synthesis of α-methylene-γ-butyrolactones from Baylis–Hillman adducts via an In-mediated Barbier reaction and stereoselective lactonization under MeSO2Cl/Et3N conditions
  作者：Bo Ram Park、Ko Hoon Kim、Jae Nyoung Kim

  DOI：10.1016/j.tetlet.2010.10.077

  日期：2010.12

  An efficient synthesis of trans-α-methylene-γ-butyrolactones is disclosed from syn-homoallylic alcohols via the intramolecular mesylate displacement reaction promoted by nearby ester group under the influence of MsCl/Et3N. syn-Homoallylic alcohols were prepared via the In-mediated Barbier reaction of the bromides of Baylis–Hillman adducts.

  的有效的合成反式-α亚甲基-γ丁内酯是从公开SYN加入MsCl / ET的影响下由附近的酯基通过促进分子内的甲磺酸酯置换反应-homoallylic醇3 N.顺-Homoallylic醇通过在制备介导的Baylis–Hillman加合物的溴化物的Barbier反应。
• Baylis–Hillman chemistry: synthesis of cis- and trans-α-methylene-γ-lactones
  作者：George W. Kabalka、Bollu Venkataiah、Chunlan Chen

  DOI：10.1016/j.tetlet.2006.04.063

  日期：2006.6

  syn-Homoallylic alcohols prepared from Baylis–Hillman adducts react with CBr4/PPh3 to give trans-α-methylene-γ-lactones. Notably, the same alcohols yield the cis-α-methylene-γ-lactones in the presence of traces of p-toluenesulfonic acid.

  顺式从的Baylis-希尔曼加合物制备-Homoallylic醇与CBR反应4 / PPH 3，得到反式-α亚甲基- γ内酯。值得注意的是，在痕量对甲苯磺酸的存在下，相同的醇产生顺式-α-亚甲基-γ-内酯。
• Tailored α-methylene-γ-butyrolactones and their effects on growth suppression in pancreatic carcinoma cells
  作者：P. Veeraraghavan Ramachandran、Debarshi Pratihar、Hari Narayanan G. Nair、Matthew Walters、Sadie Smith、Michele T. Yip-Schneider、Huangbing Wu、C. Max Schmidt

  DOI：10.1016/j.bmcl.2010.09.022

  日期：2010.11

  A selected series of racemic alpha-methylene-gamma-butyrolactones (AMGBL) were synthesized via allylboration and screened against three human pancreatic cancer cell lines (Panc-1, MIA PaCa-2, and BxPC-3). This systematic study established a discernible relationship between the substitution pattern of AMGBL and their anti-proliferative activity. beta,gamma-diaryl-AMGBLs, particularly those with a trans-relationship exhibited higher potency than parthenolide and LC-1 against all three cell lines. (C) 2010 Elsevier Ltd. All rights reserved.
• Réactivité d'organozinciques allyliques β-fonctionnels γ-substitués. Préparation d'α-méthylène γ-butyrolactones β- et γ-substituées
  作者：François Lambert、Bernard Kirschleger、Jean Villiéras

  DOI：10.1016/0022-328x(91)83172-z

  日期：1991.3

  Stable organozinc compounds derived from alkyl 3-alkyl 2-(bromomethyl) propenoates reacted with ketones and aldehydes to give alpha-methylene gamma-butyrolactones in excellent yields. Different reaction parameters were studied and some transition states were proposed.