(E)-3-methyl-1-phenylhexa-1,5-dien-3-ol | 100840-12-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: (E)-3-methyl-1-phenylhexa-1,5-dien-3-ol
• 英文别名: (1E)-3-methyl-1-phenyl-1,5-hexadien-3-ol；(1E)-3-methyl-1-phenylhexa-1,5-dien-3-ol
• CAS: 100840-12-8
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: BXMXCBXRCIPSMO-PKNBQFBNSA-N

物化性质

• 沸点：
  321.3±21.0 °C(Predicted)
• 密度：
  0.995±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-3-methyl-1-phenylhexa-1,5-dien-3-ol 在 Schwartz's reagent 、 sodium hydride 作用下， 以 四氢呋喃 、 二氯甲烷 、 mineral oil 为溶剂， 反应 1.58h， 生成 1-methyl-3-phenylcyclohexene
  参考文献：
  名称：

  通过顺序加氢锆/脱氧环化反应由二烯基醚合成1,3-二取代的环己烯

  摘要：

  描述了从含有潜在的亲电子烯丙基片段的锆茂获得1，3-二取代的环己烯的方法。需要特定的构象，6-内-trig环化是基于TMSOTf介导的稳定碳正离子化。

  DOI：

  10.1039/c8ob02925c
• 作为产物：
  描述：

  苯甲醛 在 morpholinium trifluoroacetate 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 (E)-3-methyl-1-phenylhexa-1,5-dien-3-ol
  参考文献：
  名称：

  Design, synthesis and in vitro evaluation against human cancer cells of 5-methyl-5-styryl-2,5-dihydrofuran-2-ones, a new series of goniothalamin analogues

  摘要：

  The present work describes the preparation of a novel series of compounds based on the structure of goniothalamin (1), a natural styryl lactone with known cytotoxic and antiproliferative activities against a variety of cancer cell lines. A focused library of 17 goniothalamin analogues displaying the 5-methyl-2,5-dihydrofuran-2-one motif were prepared, and their cytotoxicity evaluated. While the analogues bearing methoxy and/or hydroxy groups on the aromatic moiety usually were at least three times less potent than the lead compound (1), ortho and para-trifluoromethyl analogues 10 and 11 exhibited levels of cytotoxicity similar to goniothalamin (1) against most cancer cell lines evaluated. One could suggest that the electronic effect of the trifluoromethyl group activates the inhibitor's electrophilic site via reduction of the electron density of the alpha,beta-unsaturated ester oxygen atom. These results provide new information on the structure activity relationship of these alpha,beta-unsaturated styryl lactones, thereby further focusing the design of novel candidates. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2013.06.044

文献信息

• C–O cleavage via InIII alkoxide intermediates: In situ 13C NMR analysis of the mechanism of an enantioselective in-mediated cyclopropanation reaction
  作者：Jennifer L. Slaughter、Guy C. Lloyd-Jones

  DOI：10.1016/j.tet.2020.131786

  日期：2021.1

  dibenzylideneacetone and benzylideneacetone by in situ generated allyl indium reagents in the presence of methyl mandelate as a chiral modifier has been studied by in situ 13C1H} NMR in conjunction with 13C/2H labelling and mass spectrometry. Two indium alkoxides were identified, the first arising from indium mediated allylation of the ketone, the second arising from reaction of an in situ liberated

  通过原位13 C 1 H} NMR结合13 C / 2 H标记和质量研究了原位生成的烯丙基铟在手性改性剂存在下通过原位生成的烯丙基铟试剂对二苄叉基丙酮和苄叉基丙酮进行不对称环丙烷化的机理。光谱法。鉴定出两种铟醇盐，第一种是由铟介导的酮的烯丙基化产生的，第二种是由LiI介导的原位释放的均烯丙基与过量的烯丙基铟试剂的反应产生的。在酸化过程中，氧的质子化导致C–O而不是In–O裂解，并且初始的叔烯丙基阳离子被约90％的si立体选择性烯丙基化 通过假定为扁桃酸酯螯合的铟烯丙基试剂进行选择性。
• Generation of allyl Grignard reagents via titanocene-catalyzed activation of allyl halides
  作者：Lauren M. Fleury、Brandon L. Ashfeld

  DOI：10.1016/j.tetlet.2010.02.144

  日期：2010.5

  A protocol for the generation of allyl Grignard reagents via the catalytic activation of allyl halides is described herein. Subsequent nucleophilic addition to carbonyl derivatives provided the desired homo allylic alcohols in excellent yields (84–99%). Evidence suggests that titanocene dichloride catalyzes the formation of an allyl Grignard species which reacts solely with the carbonyl electrophile

  本文描述了通过烯丙基卤的催化活化产生烯丙基格氏试剂的方案。随后的亲核加成羰基衍生物提供了所需的均烯丙基醇，产率极高（84-99％）。有证据表明，二茂钛二氯化物催化烯丙基格氏试剂的形成，该烯丙基格利雅试剂仅与羰基亲电试剂反应，这完全不存在Würtz偶联现象。该方法在高反应性有机金属试剂的产生中将具有广泛的适用性。
• A General Catalytic Allylation Using Allyltrimethoxysilane
  作者：Shingo Yamasaki、Kunihiko Fujii、Reiko Wada、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1021/ja0262582

  日期：2002.6.1

  mild catalytic allylation of carbonyl compounds, applicable to aldehydes, ketones, and imines is developed using allyltrimethoxysilane as the allylating reagent. The reaction proceeds smoothly with 1-10 mol % of CuCl and TBAT in THF at ambient temperature. Mechanism studies indicated that the copper alkoxide, allylfluorodimethoxysilane, and allyltrimethoxysilane are essential to promote the reaction

  使用烯丙基三甲氧基硅烷作为烯丙基化试剂开发了适用于醛、酮和亚胺的羰基化合物的一般和温和的催化烯丙基化反应。在环境温度下，在 THF 中加入 1-10 mol% 的 CuCl 和 TBAT 使反应顺利进行。机理研究表明，铜醇盐、烯丙基氟二甲氧基硅烷和烯丙基三甲氧基硅烷对于有效促进反应至关重要。使用烯丙基硅烷将反应初步扩展到酮的第一次催化对映选择性烯丙基化，使用 CuCl-p-tol-BINAP-TBAT 催化剂（15 mol%）从苯乙酮中产生了 61% ee 的产物。
• Cooperative Titanocene and Phosphine Catalysis: Accelerated C–X Activation for the Generation of Reactive Organometallics
  作者：Lauren M. Fleury、Andrew D. Kosal、James T. Masters、Brandon L. Ashfeld

  DOI：10.1021/jo301726v

  日期：2013.1.18

  transmetalation approach toward the generation of Grignard and organozinc reagents mediated by a titanocene catalyst. This method enables the metalation of functionalized substrates without loss of functional group compatibility. Allyl zinc reagents and allyl, vinyl, and alkyl Grignard reagents were generated in situ and used in the addition to carbonyl substrates to provide the corresponding carbinols in yields

  本文介绍的研究描述了一种通过钛茂催化剂介导的格氏试剂和有机锌试剂的还原性过渡金属化方法。该方法能够在不损失官能团相容性的情况下金属化官能化的基材。烯丙基锌试剂和烯丙基，乙烯基和烷基格氏试剂原位生成，并用于加成羰基底物，以提供相应的甲醇，收率高达99％。研究发现，膦配体可有效地促进还原性金属转移反应，从而在低至−40°C的温度下实现C–X键的金属化。在手性二胺和氨基醇的存在下进行反应导致醛的对映选择性烯丙基化。
• Allylation of Unactivated Ketones by Tetraallyltin Accelerated by Phenol. Application to Asymmetric Allylation Using a Tetraallyltin-BINOL System
  作者：Makoto Yasuda、Noriko Kitahara、Tatsuya Fujibayashi、Akio Baba

  DOI：10.1246/cl.1998.743

  日期：1998.8

  The tetraallyltin-phenol system was mild and effective for allylation of unactivated ketones, giving tertiary alcohols in high yields. The asymmetric allylation was achieved by a tetraallyltin-homochiral BINOL (1,1′-bi-2-naphthol) system. The addition of methanol raised the enantioselectivity to afford the tertiary homoallylic alcohol up to 60% ee.

  四烯丙基锡-苯酚体系温和而有效地实现了未活化酮的烯丙基化反应，高产率地得到叔醇。通过四烯丙基锡-同手性BINOL（1,1'-双-2-萘酚）体系实现了不对称烯丙基化反应。加入甲醇后，提高了对映选择性，得到了高达60%对映体过量（ee）的叔同烯丙基醇。