4-phenyl-1-(triphenylphosphoranylidene)-(3E)-buten-2-one | 98749-52-1

• 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: 4-phenyl-1-(triphenylphosphoranylidene)-(3E)-buten-2-one
• 英文别名: (E)-2-oxo-4-phenylbut-3-enylidene(triphenyl)phosphorane；4-Phenyl-1-(triphenylphosphoranyliden)-(E)-3-buten-2-on；cinnamoylmethylene(triphenyl)phosphorane；cinnamoyl methylenetriphenylphosphorane；(E)-4-phenyl-1-(triphenyl-lambda5-phosphanylidene)but-3-en-2-one；(E)-4-phenyl-1-(triphenyl-λ5-phosphanylidene)but-3-en-2-one
• CAS: 98749-52-1；98749-53-2
• 化学式: C₂₈H₂₃OP
• 分子量: 406.464
• InChiKey: PJQGYSKPYFOBNV-QURGRASLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-phenyl-1-(triphenylphosphoranylidene)-(3E)-buten-2-one 在 sodium methylate 、 potassium carbonate 作用下， 以 甲醇 、 丙酮 、 苯 为溶剂， 反应 0.08h， 生成 2-[(E)-1-ethoxy-3-phenyl-prop-2-enylidene]-4,5-dimethyl-cyclopent-4-ene-1,3-dione
  参考文献：
  名称：

  Synthesis, Antifungal Activity, and Structure−Activity Relationships of Coruscanone A Analogues

  摘要：

  Coruscanone A, a plant-derived cyclopentenedione derivative, showed potent in vitro antifungal activity against Candida albicans and Cryptococcus neoformans comparable to amphotericin B and fluconazole. A series of analogues have been synthesized by modification of the cyclopentenedione ring, the enolic methoxy functionality, and the side chain styryl moiety of this natural product lead. A structurally close 1,4-benzoquinone analogue was also prepared. All the compounds were examined for their in vitro activity against major opportunistic fungal pathogens including C. albicans, C. neoformans, and Aspergillus fumigatus and fluconazole-resistant C. albicans strains, with several analogues demonstrating potent antifungal activity. Structure-activity relationship studies indicate that the 2-methoxymethylenecyclopent-4-ene-1,3-dione structural moiety is the pharmacophore responsible for the antifungal activity of this class of compounds while the side chain styryl-like moiety plays an important complementary role, presumably contributing to target binding.

  DOI：

  10.1021/jm061123i
• 作为产物：
  描述：

  (E)-1-bromo-4-phenylbut-3-en-2-one 在 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 2.0h， 生成 4-phenyl-1-(triphenylphosphoranylidene)-(3E)-buten-2-one
  参考文献：
  名称：

  Antifungal Cyclopentenediones from Piper coruscans

  摘要：

  Coruscanones A and B, two new antifungal cyclopentenedione derivatives, have been isolated from Piper coruscans and their structures elucidated by spectroscopic and chemical methods. Coruscanone A exhibits significant antifungal activity against Candida albicans and its azole-resistant strains and may serve as a template for a new class of antifungal agents.

  DOI：

  10.1021/ja048081c

文献信息

• N‐Heterocyclic Carbene Catalyzed (5+1) Annulations Exploiting a Vinyl Dianion Synthon Strategy
  作者：Xuan B. Nguyen、Yuji Nakano、Nisharnthi M. Duggan、Lydia Scott、Martin Breugst、David W. Lupton

  DOI：10.1002/anie.201905475

  日期：2019.8.12

  Direct polarity inversion of conjugate acceptors provides a valuable entry to homoenolates. N‐heterocyclic carbene (NHC) catalyzed reactions, in which β‐unsubstituted conjugate acceptors undergo homoenolate formation and C−C bond formation twice, have been developed. Specifically, the all‐carbon (5+1) annulations give a range of mono‐ and bicyclic cyclohexanones (31 examples). In the first family of

  共轭受体的直接极性反转提供了一个有价值的进入均烯酸酯的途径。已经开发出了N-杂环卡宾（NHC）催化的反应，其中β-未取代的共轭受体经历了均烯酸酯形成和C-C键形成两次。具体而言，全碳（5 + 1）环空给出了一系列单环和双环环己酮（31个示例）。在第一个环族中，束缚在二乙烯基酮上的β-未取代的丙烯酸酯会进行环异构化，从而提供六氢茚和四氢化萘。在第二部分中，部分未束缚的底物经历分子间（5 + 1）环合反应，其中涉及二聚化，然后进行环异构化。尽管前者不可能实现对映选择性，但后者被证明是可行的，从而可以生产出高水平的对映体纯度的环己酮（大多数> 95：5 er）和非对映选择性（> 20：1 dr）。还报道了衍生化和机理研究。
• Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 6. Pyrolysis of substituted cinnamoyl ylides as a route to conjugated enynes
  作者：R. Alan Aitken、Christine Boeters、John J. Morrison

  DOI：10.1039/p19940002473

  日期：——

  The substituted cinnamoyl ylides 6 and 7, readily prepared in one step from the quaternary phosphonium salts 8 and cinnamoyl chlorides 9, undergo extrusion of Ph3PO upon FVP to give the 1,3-enynes 12 and 13 in moderate yield. At 500 °C there is little double bond isomerisation, but at 700 °C this does occur to give almost 1:1 mixtures of E and Z isomers. In a few cases, including those with a nitrophenyl

  由季phospho盐8和肉桂酰氯9一步制备的取代肉桂酸酯基化物6和7在FVP上经过Ph 3 PO挤出，以中等收率得到1,3-烯炔12和13。在500°C下几乎没有双键异构化，但是在700°C时确实发生了几乎1：1的E和Z混合物异构体。在少数情况下，包括存在硝基苯基的情况，收率很低或反应完全失败。通过使用酯稳定的内酯来改善1-苯基丁烯的不良产率的尝试仅部分成功，因为失去酯基所需的苛刻条件导致明显的异构化为萘。报告了20个炔的完全归属的13 C NMR光谱。已经制备了一个异构体β，γ-不饱和-δ-氧代酰化物的例子，14，发现在700°C下FVP上的Ph 3 P损失，从而以低收率得到了茚和苯。
• Kinetic Resolution of Allylic Alcohol with Chiral BINOL-Based Alkoxides: A Combination of Experimental and Theoretical Studies
  作者：Yidong Liu、Song Liu、Dongmei Li、Nan Zhang、Lei Peng、Jun Ao、Choong Eui Song、Yu Lan、Hailong Yan

  DOI：10.1021/jacs.8b12796

  日期：2019.1.16

  enantioselective catalytic kinetic resolution of allylic alcohols through asymmetric isomerization with chiral BINOL derivatives-based alkoxides as bifunctional Brønsted base catalysts were described in the study. A number of chiral BINOL derivatives-based alkoxides were synthesized, and their structure-enantioselectivity correlation study in asymmetric isomerization identified a promising chiral Brønsted

  该研究描述了使用手性 BINOL 衍生物基醇盐作为双功能 Brønsted 碱催化剂通过不对称异构化对烯丙醇进行对映选择性催化动力学拆分的开发和表征。合成了许多基于手性 BINOL 衍生物的醇盐，它们在不对称异构化中的结构-对映选择性相关性研究确定了一种有前途的手性 Brønsted 碱催化剂，它提供了各种手性仲烯丙醇（ee 高达 99%，S 因子高达 >200 ）。在机理研究中，醇盐物种被确定为活性物种，而 BINOL 的酚基通过手性 Brønsted 碱催化剂和底物之间的氢键极大地影响了高反应性和对映选择性。该策略是第一个通过对映选择性无过渡金属碱催化异构化成功合成各种手性仲烯丙醇的策略。生物活性天然产物 (+)-veraguensin 的合成证明了该策略的适用性。
• Novel cyclopentenedione antifungal compounds and methods for their use
  申请人：Li Xing-Cong

  公开号：US20050215648A1

  公开（公告）日：2005-09-29

  Compounds and methods useful in the control, treatment, and prevention of fungal activity, of the following formula: where R 1-3 are independently H, alkyl, methyl, acyl, halogen, phenyl, R 4 is H, alkyl, methyl, acyl, alkoxy, halogen, phenyl provided that when R 3 is methyl and R 4 is H, R 1 and R 2 are not both H; and stereoisomers, analogs, and pharmaceutically acceptable salts thereof.

  在控制、治疗和预防真菌活性方面有用的化合物和方法，具有以下化学式：其中R1-3独立地是H、烷基、甲基、酰基、卤素、苯基，R4是H、烷基、甲基、酰基、烷氧基、卤素、苯基，但当R3是甲基且R4是H时，R1和R2不同时为H；以及其立体异构体、类似物和药用可接受的盐。
• Catalytic Allylation of Stabilized Phosphonium Ylides with Primary Allylic Amines
  作者：Xian-Tao Ma、Yong Wang、Rui-Han Dai、Cong-Rong Liu、Shi-Kai Tian

  DOI：10.1021/jo401736k

  日期：2013.11.1

  A range of ketone-stabilized phosphonium ylides were allylated with high regioselectivity by primary allylic amines in the presence of 5 mol % Pd(PPh3)4 and 10 mol % B(OH)3, and subsequent one-pot Wittig olefination gave structurally diverse α,β-unsaturated ketones in good to excellent overall yields with excellent E selectivity. The one-pot allylation/olefination reaction was extended to ester- and

  在5 mol％Pd（PPh 3）4和10 mol％B（OH）3的存在下，通过伯烯丙基胺以高区域选择性将一系列酮稳定化的磷鎓烷基化，然后进行一锅Wittig烯化反应，从而获得结构上的多样性α，β-不饱和酮，具有优异的E选择性，具有良好的总收率或优异的总收率。通过用TsOH取代B（OH）3，将一锅烯丙基化/烯烃化反应扩展到酯和腈稳定的phospho，然后以适当的总收率得到相应的α，β-不饱和酯和腈。