methyl (2E)-2-(hydroxymethyl)-2-butenoate | 28127-64-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: methyl (2E)-2-(hydroxymethyl)-2-butenoate
• 英文别名: (E)-methyl 2-(hydroxymethyl)but-2-enoate；methyl (E)-2-(hydroxymethyl)-2-butenoate；2-Hydroxymethyl-trans-crotonsaeure-methylester；methyl (E)-2-(hydroxymethyl)but-2-enoate
• CAS: 28127-64-2
• 化学式: C₆H₁₀O₃
• 分子量: 130.144
• InChiKey: DBYBUUKUKNOJQU-HWKANZROSA-N

物化性质

• 沸点：
  202.0±23.0 °C(Predicted)
• 密度：
  1.066±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (2E)-2-(hydroxymethyl)-2-butenoate 在 咪唑 、 manganese(IV) oxide 、 二异丁基氢化铝 、 potassium carbonate 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 methyl (1S,2S,5R)-4-<<(tert-butyldiphenylsilyl)oxy>methyl>-1-hydroxy-5-methyl-2-<2'-methyl-3'-<(tert-butyldimethylsilyl)oxy>-1'(E)-propen-1'-yl>3-cyclohexene-1-carboxylate
  参考文献：
  名称：

  Kijanolide上半部分的非对映选择性合成

  摘要：

  描述了焦亚醇胺的上半部分（4）的高度非对映选择性的合成。关键步骤是三烯6和手性亲二烯体6的exo和非对映体选择性Diels-Alder反应。

  DOI：

  10.1016/s0040-4039(00)70684-8
• 作为产物：
  描述：

  3-羟基-2-亚甲基丁酸甲酯 在 N-溴代丁二酰亚胺(NBS) 、 2,3-二巯基丁二酸 、 sodium acetate 、 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 34.0h， 生成 methyl (2E)-2-(hydroxymethyl)-2-butenoate
  参考文献：
  名称：

  A highly diastereo- and enantioselective synthesis of the top half of kijanolide

  摘要：

  A highly diastereo- and enantioselective synthesis of spirotetronate 4 corresponding to the top half of kijanolide is reported. This synthesis features the novel exo-selective Diels-Alder reaction of triene 6 and the chiral, nonracemic dienophiles (R)-7 and (R)-8. The reaction of 6 and (R)-7 produced a mixture of the desired exo cycloadduct 28, the unexpected exo diastereofacial isomer 29, and a minor amount of the endo cycloadduct 30. However, the Diels-Alder reaction of 6 and dienophile (R)-8 with the more sterically demanding tert-butyl substituent provided a 13-14:1 mixture of exo cycloadduct 38 and endo isomer 39; the exo diastereofacial isomer corresponding to 29 was not observed. Elaboration of 28 and 38 to spirotetronate 4 proceeded by way of the Dieckmann cyclization of alpha-acetoxy ester 5.

  DOI：

  10.1021/jo00060a035

文献信息

• An approach toward the total synthesis of subergorgic acid
  作者：John C. Gilbert、Jiandong Yin

  DOI：10.1016/j.tet.2008.04.005

  日期：2008.6

  Ireland–Claisen rearrangement of a substituted alkenyl cyclopentanecarboxylate provided a monocyclic isomer containing the proper stereochemistry for four of the five stereogenic centers in subergorgic acid. Efforts to construct the additional rings in the molecule were thwarted as a result of steric and other factors. The results provide insights regarding the Ireland–Claisen rearrangement in five-membered

  取代链烯基环戊烷羧酸的爱尔兰－克莱森重排提供了一种单环异构体，该异构体具有适当的立体化学，这五个立体异构中心位于五个金属中。由于空间和其他因素，阻碍了在分子中构建额外环的努力。结果提供了有关五元环系统中爱尔兰-克莱森重排的见解。如本文报道的，由立体和立体电子要求高的系统形成螺环化合物具有作为合成天然和非天然产物中此类亚单元的一般策略的潜力。
• Indium-mediated allylation of carbonyl compounds with an allylic bromide in aqueous media: anomalous syn-diastereoselectivity regardless of allylic bromide geometry
  作者：Teck-Peng Loh、Zheng Yin、Hong-Yan Song、Kee-Leng Tan

  DOI：10.1016/s0040-4039(02)02773-9

  日期：2003.1

  Anomalous syn-diastereoselectivity of indium-mediated coupling of aldehydes with bromides Z-3b and E-3b is reported. The reaction afforded high syn selectivity regardless of the allylic bromide geometry. Preliminary studies on the enantioselective indium-mediated allylation were attempted and found to give the desired products in moderate yield with high syn selectivity and enantioselectivity.

  异常顺醛与溴化物铟-介导的偶联的-diastereoselectivity ž -图3b和ë -图3b报道。不管烯丙基溴的几何形状如何，该反应均提供高的顺式选择性。尝试了对映选择性铟介导的烯丙基化的初步研究，发现以中等收率获得了所需的产物，同时具有高的顺式选择性和对映选择性。
• Die<i>Wohl-Ziegler</i>-Bromierung von Tiglin- und Angelika-säureestern
  作者：A. Löffler、R. J. Pratt、H. P. Rüesch、André S. Dreiding

  DOI：10.1002/hlca.19700530221

  日期：——

  size of the ester alkoxy group. The same products were obtained from the NBS treatment of methyl angelate (2b). This NBS-bromination appears to be thermodynamically controlled, since both angelic and tiglic acid as well as their methyl esters were brought into equilibrium (1 ⇆ 2 = > 9:1) with catalytic amounts of NBS.

  tigtig甲酯（1b）的Wohl - Ziegler溴化（N-溴代琥珀酰亚胺= NBS）得到了γ-溴代甲基丙烯酸酯（3b）和β'-溴代甲基丙烯酸酯（5b）的2：1混合物。γ-溴化与β'-溴化的比率不受溶剂，催化剂或酯烷氧基基团尺寸变化的影响。从NBS处理的当归酸甲酯（2b）获得了相同的产品。这种NBS溴化似乎是热力学控制的，因为当量的NBS催化使天使酸和tiglic酸及其甲基酯达到平衡（1⇆2 => 9：1）时。
• Fluorine-containing compounds and polymers derived therefrom
  申请人：——

  公开号：US20030109626A1

  公开（公告）日：2003-06-12

  Provided are fluorine-containing compounds, and polymers derived therefrom, for use in compositions used for treating textile substrates. Also provided are methods of making fluorine-containing compounds and polymers derived therefrom, compositions comprising the compounds and/or polymers of the present invention, methods of treating substrates, and the treated products derived therefrom.

  提供含氟化合物和由此衍生的聚合物，用于处理纺织物基材的组合物。还提供制备含氟化合物和由此衍生的聚合物的方法，包括本发明化合物和/或聚合物的组合物，处理基材的方法以及由此衍生的处理产品。
• Catalytic Enantioselective Total Synthesis of (+)-Torrubiellone C
  作者：Henning J. Jessen、Andreas Schumacher、Fabian Schmid、Andreas Pfaltz、Karl Gademann

  DOI：10.1021/ol201692h

  日期：2011.8.19

  Silyl-protected (R)-methyl 2-(hydroxymethyl)butanoate was obtained by an enantioselective Ir-catalyzed hydrogenation In high yield and selectivity. Elaboration of this building block via Takai and Stille reactions gave a protected hydroxy polyene chain, which was coupled to a 5-hydroxyphenyl-4-hydroxy-2-pyridone derivative by a modified Horner-Wadsworth-Emmons reaction. Deprotection gave synthetic (+)-torrublelione C, which led to the assignment of the configuration of the natural product as (R).