ethyl 4-methyl-3,6-dihydro-2H-pyran-2-carboxylate | 27944-73-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: ethyl 4-methyl-3,6-dihydro-2H-pyran-2-carboxylate
• CAS: 27944-73-6
• 化学式: C₉H₁₄O₃
• 分子量: 170.208
• InChiKey: SBENLRUVWAJUTN-UHFFFAOYSA-N

物化性质

• 沸点：
  219.4±40.0 °C(Predicted)
• 密度：
  1.044±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 4-methyl-3,6-dihydro-2H-pyran-2-carboxylate 在 lithium hydroxide monohydrate 作用下， 以 四氢呋喃 、 乙醚 、 水 为溶剂， 反应 3.5h， 生成
  参考文献：
  名称：

  通过串联C–H氧化/ oxa- [3,3]应付重排/醛醇环化，改进了8-氧杂双环[3.2.1]辛烷的合成

  摘要：

  的串联C-H的氧化/氧杂[3,3] Cope重排/醛用T促进烯丙基甲硅烷基醚的反应+ BF 4 -（TEMPO含氧铵四氟硼酸盐）/ ZnBr 2已研制成功，允许-8-氧杂双环的高效的施工[ 3.2.1]辛烷及其类似物具有广泛的底物范围。

  DOI：

  10.1039/c7cc08511g
• 作为产物：
  描述：

  乙醛酸乙酯 、 天然橡胶 在 bismuth(lll) trifluoromethanesulfonate 作用下， 以 正戊烷 为溶剂， 反应 72.0h， 生成 ethyl 4-methyl-3,6-dihydro-2H-pyran-2-carboxylate 、 Ethyl 2-hydroxy-4-methylidenehex-5-enoate
  参考文献：
  名称：

  Le Triflate de Bismuth(III) Comme Catalyseur Dans la Reaction de Carbonyl-Diels-Alder

  摘要：

  在三氟甲磺酸铋 (III) 存在下，羰基化的亲电子试剂（甲基草酸乙酯或乙醛酸乙酯）和普通二烯选择性地（60-100）导致杂羰基-Diels-Alder 反应与烯反应产物。Bi(OTf) 3 表现出很强的催化活性并且在温和的条件下反应。En présence de triflate de bismuth(III) le mésoxalate et le glyoxylate d'éthyle réagissent avec des diènes usuels pour donner un mélange de carbonyl-Diels-Alder et du produit de la ène réaction。Bi(OTf) 3 présente une forte activité catalytique et réagit dans des conditions douces。

  DOI：

  10.1080/10426500210673

文献信息

• The carbonyl-Diels-Alder reaction catalyzed by bismuth (III) chloride
  作者：Hélène Robert、Bernard Garrigues、Jacques Dubac

  DOI：10.1016/s0040-4039(97)10791-2

  日期：1998.3

  In presence of bismuth (III) chloride, a carbonylated electrophile (ethyl mesoxalate or glyoxylate) and usual diene led selectively (65 to 100%) the hetero carbonyl-Diels-Alder reaction with the ene reaction product. BiCl3 exhibits strong catalytic activity and, compared with previous literature, reacts under mild conditions.

  在氯化铋（III）的存在下，羰基化的亲电试剂（中草酸乙酯或乙醛酸乙酯）和通常的二烯选择性地（65％至100％）导致杂羰基-Diels-Alder反应与烯反应产物。BiCl 3表现出很强的催化活性，并且与以前的文献相比，在温和的条件下反应。
• Glyoxylate-Ene Reaction Catalyzed by Ln(OTf)3
  作者：Changtao Qian、Taisheng Huang

  DOI：10.1016/s0040-4039(97)01536-0

  日期：1997.9

  Yb(OTf)(3), can catalyze the glyoxylate-ene reaction effectively as a water-stable and reusable catalyst. Moreover, the selectivity of DA product or ene product can be adjusted by solvents in the reaction of glyoxylates with a diene (isoprene). In the presence of chiral ytterbium complexes generated in situ from Yb(OTf)(3) and optical 6,6'-disubstituted binaphthols, methyl glyoxylate smoothly reacts with alpha-methyl styrene to afford alpha-hydroxyl esters in modest optical yields. (C) 1997 Elsevier Science Ltd.
• Asymmetric Hetero Diels−Alder Reaction Catalyzed by Chiral Cationic Palladium(II) and Platinum(II) Complexes
  作者：Shuichi Oi、Eiji Terada、Kazuei Ohuchi、Tomoko Kato、Yukari Tachibana、Yoshio Inoue

  DOI：10.1021/jo9906680

  日期：1999.11.1

  The hetero Diels-Alder reaction of nonactivated conjugated dienes 1 with arylglyoxals 2 and glyoxylate esters 7 proceeded enantioselectively in the presence of a catalytic amount of cationic chiral BINAP-palladium or -platinum complexes and 3 Angstrom molecular sieves (MS3A). The addition of MS3A effectively improved the enantioselectivity of the reaction. Excellent ee's were obtained from the reactions of 2,3-dimethyl-1,3-butadiene (1a) and 1,3-cyclohexadiene (1d) with dienophiles 2 and 7. The square-planar structure of [Pd(S-BINAP)(PhCN)(2)](PF6)(2) was determined by X-ray diffraction, and a chiral induction model involving the square-planar palladium complex coordinated with BINAP and a dienophile is proposed.
• Asymmetric hetero Diels-Alder reactions and ene reactions catalyzed by chiral copper(II) complexes
  作者：Mogens Johannsen、Karl Anker Joergensen

  DOI：10.1021/jo00123a007

  日期：1995.9

  A new copper(II) bisoxazoline-catalyzed reaction of glyoxylate esters with dienes leading to the hetero Diet-Alder product and the ene product in high yield and with a high enantiomeric excess (ee) has been developed. The hetero Diels-Alder product:ene product ratio is in the range 1:0.6 to 1:1.8 and is dependent on both the chiral ligand attached to the metal, the glyoxylate ester, and the reaction temperature. The scope of the copper(II) bisoxazoline-catalyzed reaction of glyoxylate esters with dienes is demonstrated by the reaction of a variety of different dienes with ethyl and isopropyl glyoxylate, and it is shown that a simple substrate such as 1,3-butadiene reacts to give the hetero Diels-Alder product in 55% yield with an ee of 87%. Furthermore, the synthetic application of the reaction is demonstrated by the synthesis of a highly interesting synthon for sesquiterpene lactones in high yield and diastereoselectivity, and with a very high ee from 1,3-cyclohexadiene and ethyl glyoxylate using a copper(II) bisoxazoline as the catalyst. A mechanism for the hetero Diels-Alder reaction, which accounts for the enantioselectivity in the reactions, is proposed.
• Improved synthesis of 8-oxabicyclo[3.2.1]octanes <i>via</i> tandem C–H oxidation/oxa-[3,3] Cope rearrangement/aldol cyclization
  作者：Lin Liu、Hai-Long Cheng、Wen-Qiang Ma、Si-Hua Hou、Yong-Qiang Tu、Fu-Min Zhang、Xiao-Ming Zhang、Shao-Hua Wang

  DOI：10.1039/c7cc08511g

  日期：——

  A tandem C–H oxidation/oxa-[3,3] Cope rearrangement/aldol reaction of allylic silylethers promoted by T+BF4−(tempo oxoammonium tetrafluoroborate)/ZnBr2 has been successfully developed allowing the efficient construction of 8-oxabicyclo[3.2.1]octanes and their analogs with a wide substrate scope.

  的串联C-H的氧化/氧杂[3,3] Cope重排/醛用T促进烯丙基甲硅烷基醚的反应+ BF 4 -（TEMPO含氧铵四氟硼酸盐）/ ZnBr 2已研制成功，允许-8-氧杂双环的高效的施工[ 3.2.1]辛烷及其类似物具有广泛的底物范围。