4-phenyl-2-methylenebutyrolactone | 26613-71-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 4-phenyl-2-methylenebutyrolactone
• 英文别名: 3-methylene-5-phenyldihydrofuran-2(3H)-one；2(3H)-Furanone, dihydro-3-methylene-5-phenyl-；3-methylidene-5-phenyloxolan-2-one
• CAS: 26613-71-8
• 化学式: C₁₁H₁₀O₂
• 分子量: 174.199
• InChiKey: QQZWJUGXPKGMND-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 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：

  4-phenyl-2-methylenebutyrolactone 在 copper(l) iodide 、 三丁基膦 、 叔丁基锂 作用下， 以 乙醚 为溶剂， 反应 2.0h， 生成
  参考文献：
  名称：

  Conjugate propargylation of α,β-unsaturated lactones: a solution via 1,4-addition of (Z)-2-ethoxyvinyl anion

  摘要：

  Conjugate addition of (Z)-2-ethoxyvinyl anion to alpha,beta -unsaturated lactones is best effected via Noyori-type organocopper reagents. The resulting adducts may be advanced to beta -propargyllactones or utilized in the preparation of functionalized pyridines. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)01506-9
• 作为产物：
  描述：

  3-ethoxycarbonyl-3-(phenylsulfonyl)cyclobutanol 在 锂硼氢 、 乙酸酐 、 potassium hydride 、 对甲苯磺酸 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 乙醚 、 二甲基亚砜 、 甲苯 为溶剂， 反应 20.25h， 生成 4-phenyl-2-methylenebutyrolactone
  参考文献：
  名称：

  A New Method for the Preparation of α-Methylene-γ-butyrolactones Using 3-Ethoxycarbonyl-3-(phenylsulfonyl)cyclobutanone

  摘要：

  3-乙氧羰基-3-(苯基磺酰)环丁酮与格氏试剂或芳基锂反应生成1-(烷基或芳基)-3-乙氧羰基-3-(苯基磺酰)环丁醇，该产物随后与氢化钾处理，再在ZnCl2存在下用LiBH4还原，最后依次用对甲苯磺酸或三异丙氧化铝处理，良好产率得到α-亚甲基-γ-丁内酯。

  DOI：

  10.1246/bcsj.62.1524

文献信息

• Catalytic Redox Chain Ring Opening of Lactones with Quinones To Synthesize Quinone-Containing Carboxylic Acids
  作者：Xiao-Long Xu、Zhi Li

  DOI：10.1021/acs.orglett.9b01672

  日期：2019.7.5

  Catalytic ring opening of five- to eight-membered lactones with quinones is achieved through a redox chain mechanism. With low loading of a simple metal triflate Lewis acid catalyst and a chain initiator, C–H bonds of many quinones were efficiently functionalized with carboxylic acid-containing side chains. This method also features 100% atom economy and wide substrate scope. A novel route to the anti-asthma

  五至八元内酯与醌的催化开环是通过氧化还原链机理实现的。在简单的三氟甲磺酸金属路易斯酸催化剂和链引发剂的低负载下，许多醌的C–H键被含羧酸的侧链有效地官能化。该方法还具有100％的原子经济性和广泛的底物范围。开发了一种抗哮喘药Seratrodast的新途径。机理研究表明，氧化还原链反应可能发生碳正离子中间体。
• Palladium-catalyzed carbonyl allylation by 2-(hydroxymethyl)acrylate derivatives: synthesis of α-methylene-γ-butyrolactones
  作者：Yoshiro Masuyama、Yumiko Nimura、Yasuhiko Kurusu

  DOI：10.1016/0040-4039(91)80861-y

  日期：1991.1

  Ethyl 2-(Hydroxymethyl)acrylate derivatives serve as reagents for 2-ethoxycarbonylallylation of carbonyl compounds using PdCl2(PhCN)2-SnCl2 system to produce α-methylene-γ-butyrolactones diastereoselectivity.

  2-（羟甲基）丙烯酸乙酯衍生物用作使用PdCl 2（PhCN）2 -SnCl 2体系进行羰基化合物的2-乙氧基羰基化的试剂，以产生α-亚甲基-γ-丁内酯非对映选择性。
• Reagent-controlled stereoselection in radical addition to α-methylenebutyrolactones
  作者：Hirokazu Urabe、Katsushige Kobayashi、Fumie Sato

  DOI：10.1039/c39950001043

  日期：——

  Some β- or γ-substituted α-methylenebutyrolactones are butylated with Bul and (Me3Si)3SiH to give cis-α,β- or -α,γ-disubstituted lactones in high selectivites, while the same reaction with Bu3SnH in the presence of bulky Lewis acid reverses the stereoselectivity to give a trans-disubstituted lactone as the major product.

  用Bul和（Me 3 Si）3 SiH对某些β-或γ-取代的α-亚甲基丁内酯进行丁基化处理，得到高选择性的顺式-α，β-或-α，γ-二取代的内酯，同时与Bu 3 SnH进行相同的反应在大体积存在下，路易斯酸逆转立体选择性，得到反式-二取代的内酯作为主要产物。
• A stereodivergent synthesis of β-hydroxy-α-methylene lactones via vinyl epoxides
  作者：Marion Davoust、Frédéric Cantagrel、Patrick Metzner、Jean-François Brière

  DOI：10.1039/b802310g

  日期：——

  A catalytic diastereoselective sulfonium ylide epoxidation of aldehydes furnished original vinyl epoxides, having an MBH backbone. These highly functionalised building blocks were used for a formal synthesis of the antibiotic conocandin, and opened up a stereodivergent route towards β-hydroxy-α-methylene lactones, core units of naturally occurring compounds. Under acidic conditions, the oxiranes were mainly transformed, with moderate to good yields, into transβ-hydroxy-α-methylene lactones. On the other hand, a user-friendly palladium-catalysed CO2insertion and cyclisation sequence gave the cisβ-hydroxy-α-methylene lactone counterparts along with an interesting cis–trans equilibration of the π-allyl intermediates.

  一种催化性的非对映选择性硫镛叶立德环氧化反应，将醛转化为具有MBH骨架的原始乙烯基环氧化物。这些高度功能化的构建块被用于抗生素康索坎丁的正式合成，并开辟了一条向天然化合物核心单元——β-羟基-α-亚甲基内酯的立体发散性途径。在酸性条件下，环氧化物主要发生转化，产率从中等到良好，形成反式β-羟基-α-亚甲基内酯。另一方面，一种用户友好的钯催化CO2插入和环化序列，得到了顺式β-羟基-α-亚甲基内酯及其有趣的π-烯丙基中间体的顺-反平衡。
• Catalytic, Nucleophilic Allylation of Aldehydes with 2-Substituted Allylic Acetates: Carbon–Carbon Bond Formation Driven by the Water–Gas Shift Reaction
  作者：Scott E. Denmark、Zachery D. Matesich

  DOI：10.1021/jo501004j

  日期：2014.7.3

  The ruthenium-catalyzed allylation of aldehydes with allylic acetates has been expanded to incorporate substituents at the 2-position of the allylic components. Allylic acetates bearing a variety of substituents (CO2-t-Bu, COMe, Ph, CH(OEt)2, and Me) undergo high-yielding additions with aromatic, α,β-unsaturated, and aliphatic aldehydes. The conditions of the reaction were found to be mild (75 °C,

  醛与烯丙基乙酸酯的钌催化的烯丙基化已经扩大，以在烯丙基组分的2-位引入取代基。带有多种取代基（CO 2 - t- Bu，COMe，Ph，CH（OEt）2和Me）的烯丙基乙酸酯会与芳香族，α，β-不饱和和脂肪族醛类进行高产率的加成反应。发现反应条件温和（75°C，24–48 h），仅需在40–80 psi的CO下使用2-3 mol％的十二碳三钌催化剂。水和烯丙基的化学计量比发现使用的乙酸盐对反应效率至关重要。