(E)-methyl 4-(benzo[d][1,3]dioxol-5-yl)-2-oxobut-3-enoate | 162087-78-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-methyl 4-(benzo[d][1,3]dioxol-5-yl)-2-oxobut-3-enoate
• 英文别名: (E)-4-(benzo[d][1,3]dioxol-5-yl)-2-oxobut-3-enoic acid methyl ester；methyl (E)-4-(1,3-benzodioxol-5-yl)-2-oxobut-3-enoate
• CAS: 162087-78-7
• 化学式: C₁₂H₁₀O₅
• 分子量: 234.208
• InChiKey: UTXDJHOSPYKVLE-DUXPYHPUSA-N

物化性质

• 沸点：
  372.6±42.0 °C(Predicted)
• 密度：
  1.336±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (E)-methyl 4-(benzo[d][1,3]dioxol-5-yl)-2-oxobut-3-enoate 在 magnesium(II) perchlorate 、 NO-冯-PDETMPPI 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.5h， 生成 (E)-methyl 2-(2-(1,3-dihydroisobenzofuran-5-yl)vinyl)-4-oxo-3,4-dihydro-2H-pyran-2-carboxylate
  参考文献：
  名称：

  N，N'-二氧化物/镁（II）手性配合物催化Danishefsky's Diene与α-酮酸酯和Isatins的不对称杂Diels-Alder反应

  摘要：

  丹尼谢夫斯基双烯与α酮酯和靛红的高度对映选择性的杂Diels-Alder反应已经通过使用手性实现Ñ，Ñ '二氧化物/镁II复合物。在仅0.1-0.5 mol％的催化剂存在下，一系列的底物在两个小时内转化成相应的四取代的2,3-二氢吡喃-4-酮，产率高达99％，ee大于99％  。

  DOI：

  10.1002/chem.201404144
• 作为产物：
  描述：

  胡椒醛 在 乙酰氯 、 potassium hydroxide 作用下， 以 甲醇 为溶剂， 生成 (E)-methyl 4-(benzo[d][1,3]dioxol-5-yl)-2-oxobut-3-enoate
  参考文献：
  名称：

  通过多米诺骨牌迈克尔/半缩合反应对多取代五元氧杂环的对映选择性构建的新策略

  摘要：

  报道了α-羟基苯乙酮与β，γ-不饱和α-酮酯的一种新的高对映选择性多米诺骨牌迈克尔/半缩合反应，用于合成2,2,4,5-四取代的手性四氢呋喃。用2摩尔％的分子内的双核锌AzePhenol络合物在从多齿半氮杂冠醚配体与ZnEt反应原位制备2，相应的抗在高达90％的收率得到-multisubstituted四氢呋喃产品，和98％对映体过量（EE）在0°C下放置45分钟。而且，该产物很容易转化为2,3,5-三取代的2,3-二氢呋喃，而没有任何光学活性的损失。

  DOI：

  10.1002/chem.201501655

文献信息

• Asymmetric Synthesis of Oxa‐Bridged Oxazocines through a Catalytic Rh ^II /Zn ^II Relay [4+3] Cycloaddition Reaction
  作者：Chaoran Xu、Kaixuan Wang、Dawei Li、Lili Lin、Xiaoming Feng

  DOI：10.1002/anie.201910898

  日期：2019.12.16

  oxazocines bearing three chiral carbon centers were synthesized efficiently through a bimetallic catalytic asymmetric tandem reaction of β,γ-unsaturated α-ketoesters with diazoimides. The process contained a rhodium-promoted in situ generation of isomünchnone from diazoimide decomposition, and a [4+3]-cycloaddition of β,γ-unsaturated α-ketoester catalyzed by a chiral N,N'-dioxide-ZnII complex. Ligand-accelerated

  通过β，γ-不饱和α-酮酸酯与重氮酰亚胺的双金属催化不对称串联反应有效地合成了带有三个手性碳中心的桥杂恶唑啉。该过程包括铑由重氮酰亚胺分解原位生成的异丁香酮，以及由手性N，N'-二氧化物-ZnII配合物催化的β，γ-不饱和α-酮酸酯的[4 + 3]-环加成。发现了配体加速催化，并提出了可能的过渡态模型来解释立体选择性的起源。
• Asymmetric Organocatalytic Reductive Coupling Reactions between Benzylidene Pyruvates and Aldehydes
  作者：Matthew A. Horwitz、Blane P. Zavesky、Jesus I. Martinez-Alvarado、Jeffrey S. Johnson

  DOI：10.1021/acs.orglett.5b03127

  日期：2016.1.4

  An organocatalytic three-component reductive coupling reaction between dimethyl phosphite, benzylidene pyruvates, and aldehydes is reported. A chiral triaryliminophosphorane catalyst promotes Pudovik addition, which is followed by phospha-Brook rearrangement to transiently generate enolates that are trapped stereoselectively by aldehydes. This reductive coupling provides vicinal polyfunctionalized

  报道了亚磷酸二甲酯，亚苄基丙酮酸酯和醛之间的有机催化三组分还原偶联反应。手性三芳基次膦酸酯催化剂可促进Pudovik加成，然后进行磷-布鲁克重排以瞬时生成被醛选择性立体捕获的烯醇化物。这种还原偶联从容易获得的手性起始原料中提供了邻近的多官能化立体中心，具有出色的非对映选择性，对映选择性和产率。
• Lignans.19. Total synthesis of (−)-O-dimethylsugiresinol, involving asymmetric [4+2] heterocycloaddition of a styrene with a benzylidenepyruvic ester of an α-O-silyl derivative of (D)-erythronolactone
  作者：Eric Brown、Gilles Dujardin、Mickaël Maudet

  DOI：10.1016/s0040-4020(97)00646-7

  日期：1997.7

  alpha-O-t-Butyldiphenylsilyl-(D)-erythronolactone [(+/-)-25] (a new chiral vector) was esterified with 4-methoxybenzylidene pyruvic acid (19). Eu(fod)(3) catalyzed [4+2] heterocycloaddition of the latter 1-oxabutadiene with 4-methoxystyrene (as the dienophile), afforded high yields of the endo adduct 23c with 95/5 diastereofacial ratio. Five further steps led to enantiomerically pure natural (-)-O-dimethylsugiresinol (-)-2 in 12% overall yield from the acid 19. (C) 1997 Elsevier Science Ltd.
• High yield endoselective heterocycloadditions involving benzylidenepyruvic esters as the heterodiene and an alkoxystyrene as the dienophile
  作者：Gilles Dujardin、Mickaël Maudet、Eric Brown

  DOI：10.1016/s0040-4039(00)78452-8

  日期：1994.11

  The benzylidenepyruvic esters 6, 10a-d and 11 smoothly reacted with the alkoxystyrenes 12 and 13 in refluxing hexane or toluene and in the presence of catalytic amounts of Eu(fod)(3), thus selectively lending to the endo adducts 14-21 in high yields. This represents the first examples of an efficient heterocycloaddition of styrene derivatives without using the high pressure technique. The above adducts are potential intermediates for sugiresinol 7 and related tetrahydropyran neolignans.
• New two-step sequence involving a hetero-Diels–Alder and a nonphenolic oxidative coupling reaction: a convergent access to analogs of steganacin
  作者：Mathieu Y. Laurent、Vivien Stocker、Valéry Momo Temgoua、Gilles Dujardin、Robert Dhal

  DOI：10.1016/j.tetlet.2011.01.097

  日期：2011.4

  A new family of analogs of steganacin, an important antimitotic compound, was accessed. It takes advantage of a completely stereoselective sequence of two key steps. The central dihydropyrane core is built by a highly diastereoselective and facially controlled hetero-Diels-Alder reaction. It is followed by a nonphenolic biaryl oxidative coupling with a complete atropo-stereoselectivity. It leads to a quick way to form cyclic biaryl lignans. (C) 2011 Elsevier Ltd. All rights reserved.