methyl (E)-3-methyl-4-oxopent-2-enoate | 53663-11-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl (E)-3-methyl-4-oxopent-2-enoate
• 英文别名: methyl 3-methyl-4-oxopent-2-enoate
• CAS: 53663-11-9
• 化学式: C₇H₁₀O₃
• 分子量: 142.155
• InChiKey: JDAODWYVSFNKRR-SNAWJCMRSA-N

物化性质

• 沸点：
  219.1±23.0 °C(Predicted)
• 密度：
  1.029±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (E)-3-methyl-4-oxopent-2-enoate 在 2,6-二甲基吡啶 、 正丁基锂 、 silica gel 、 三氟乙酸酐 作用下， 以 二氯甲烷 为溶剂， 反应 5.75h， 生成 2,3-dimethyl-5-methylene-4-oxo-cyclopent-2-enecarboxylic acid methyl ester
  参考文献：
  名称：

  Cyclopentannelation Reaction for Rapid Assembly of Multifunctional Products. (d,l)-Desepoxymethylenomycin a Methyl Ester

  摘要：

  The scope of the alkoxyallene cationic cyclopentannelation reaction has been examined. Non-hydrogen substituents at both C4 and C5 were required for synthetically useful yields. Whereas the cyclization appeared to be subject to steric constraints, it was relatively insensitive to electronic effects. An efficient synthesis of (d,l)- , desepoxymethylenomycin A methyl ester has been described.

  DOI：

  10.1080/00397919408011309
• 作为产物：
  描述：

  甲醇 、 3-甲基-4-氧代-2-烯酸 在 盐酸 作用下， 生成 methyl (E)-3-methyl-4-oxopent-2-enoate
  参考文献：
  名称：

  布鲁西汀和布鲁西汀醇的分离和结构鉴定，这是来自布鲁斯抗痢疾药的新的有效抗白血病类quassinoids。

  摘要：

  DOI：

  10.1021/jo00893a023

文献信息

• Biocatalytic access to nonracemic γ-oxo esters via stereoselective reduction using ene-reductases
  作者：Nikolaus G. Turrini、Răzvan C. Cioc、Daan J. H. van der Niet、Eelco Ruijter、Romano V. A. Orru、Mélanie Hall、Kurt Faber

  DOI：10.1039/c6gc02493a

  日期：——

  The asymmetric bioreduction of [small alpha],[small beta]-unsaturated [gamma]-keto esters using ene-reductases from the Old Yellow Enzyme family proceeds with excellent stereoselectivity and high conversion levels, covering a broad range of acyclic and...

  使用Old Yellow Enzyme家族的烯键还原酶对小，小β-不饱和γ-酮酸酯进行不对称生物还原，具有出色的立体选择性和高转化率，涵盖了广泛的无环和...
• Acylammonium Salts as Dienophiles in Diels–Alder/Lactonization Organocascades
  作者：Mikail E. Abbasov、Brandi M. Hudson、Dean J. Tantillo、Daniel Romo

  DOI：10.1021/ja501005g

  日期：2014.3.26

  α,β-Unsaturated acylammonium salts, generated in situ from commodity acid chlorides and a chiral isothiourea organocatalyst, comprise a new and versatile family of chiral dienophiles for the venerable Diels–Alder (DA) cycloaddition. Their reactivity is unveiled through a highly diastereo- and enantioselective Diels–Alder/lactonization organocascade that generates cis- and trans-fused bicyclic γ- and

  α,β-不饱和酰基铵盐是由商品酰氯和手性异硫脲有机催化剂原位生成的，包括用于古老的 Diels-Alder (DA) 环加成的新型多功能手性亲二烯体家族。它们的反应性是通过高度非对映选择性和对映选择性 Diels-Alder/内酯化有机级联来揭示的，该有机级联产生具有多达四个连续立体中心的顺式和反式融合双环 γ- 和 δ-内酯。此外，描述了 DA 启动的立体发散有机级联的第一个例子，它提供了在生物活性化合物中发现的复杂支架。通过计算研究使立体选择性的起源合理化。此外，该方法的实用性通过对冰糖苷核心结构的简洁方法和 fraxinellone 的正式合成得到证明，
• On the regioselectivity in nitrone cycloadditions to γ-oxo α,β-unsaturated esters
  作者：Ramón Alibés、Félix Busqué、Pedro de March、Marta Figueredo、Josep Font、Teodor Parella

  DOI：10.1016/s0040-4020(98)00628-0

  日期：1998.9

  The 1,3-dipolar cycloadditions of the cyclic nitrones 1 and 2 to several γ-oxo α,β-unsaturated esters, 5–10, are reported. A strong predominance of the regioisomers with the oxygen atom of the dipole attached to the β-ester position is observed. This high regioselectivity is attributed to steric factors. The reduction of the carbonyl group of some of the major cycloadducts is a good yielding procedure

  据报道，环状硝酮1和2的1，3-偶极环加成有几种γ-氧代α，β-不饱和酯5-10。观察到区域异构体的强烈优势是偶极子的氧原子附着在β-酯位置上。这种高区域选择性归因于空间因素。某些主要环加合物的羰基还原是制备某些羟基衍生物的好方法，这些羟基衍生物在相同硝酮与相应的γ-羟基α，β的环加成中并未形成或仅以较小的立体异构体形式获得。 -不饱和酯。
• COORDINATION COMPLEX SYSTEM COMPRISING TAUTOMERIC LIGANDS
  申请人：Reek Joost Nikolaas Hendrik

  公开号：US20110003959A1

  公开（公告）日：2011-01-06

  The invention relates to a coordination complex system comprising a ligand having the formula: R 1 —SO 2 —NH—P (XR 2 ) 2 (1a); or R 1 —SO 2 —N═PH (XR 2 ) 2 (1b); or R 1 —SO(OH)═N—P(XR 2 ) 2 (1c); wherein X is independently O, S, NH, or a bond; R 1 and R 2 are independently selected from hydrogen and substituted or unsubstituted alkyl or aryl; wherein at least one equivalent of the ligand is complexed to an equivalent of a metal selected from a transition metal and lanthanide. The invention also relates to the use of said coordination complexes as catalysts in the hydroformylation, hydrogenation, transfer hydrogenation, hydrocyanation, polymerization, isomerization, carbonylation, cross-coupling, metathesis, CH activation, allylic substitution, aldol condensation, or Michael addition.

  本发明涉及一种配位复合物系统，其包括具有以下式子的配体：R1—SO2—NH—P(XR2)2(1a)；或R1—SO2—N═PH(XR2)2(1b)；或R1—SO(OH)═N—P(XR2)2(1c)；其中X独立地为O，S，NH或键；R1和R2独立地选择氢和取代或未取代的烷基或芳基；其中至少一个配体当量与从过渡金属和镧系金属中选择的金属当量结合。本发明还涉及所述配位复合物在氢甲酰化、加氢、转移加氢、加氰、聚合、异构化、羰基化、交叉偶联、交换反应、CH活化、烯丙基取代、醛缩合或迈克尔加成中作为催化剂的用途。
• US8283276B2
  申请人：——

  公开号：US8283276B2

  公开（公告）日：2012-10-09