Methyl 2-<(methoxallyl)oxy>acetate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 肽模拟物
• 英文名称: Methyl 2-<(methoxallyl)oxy>acetate
• 英文别名: 1-methoxy-1-oxo-2-propanyl methyl oxalate；1-methoxy-1-oxopropan-2-yl methyl oxalate；2-O-(1-methoxy-1-oxopropan-2-yl) 1-O-methyl oxalate
• 化学式: C₇H₁₀O₆
• 分子量: 190.153
• InChiKey: NUOKBNCXFULCPE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Methyl 2-<(methoxallyl)oxy>acetate 、 N-Boc-4-碘苯胺 在 吡啶 、 nickel(II) iodide 、 2-(4,5-二氢-1H-咪唑-2-基)-吡啶 、 magnesium chloride 、 锌 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 12.0h， 以72%的产率得到methyl 2-(4-((tert-butoxycarbonyl)amino)phenyl)propanoate
  参考文献：
  名称：

  Ni-Catalyzed Reductive C–O Bond Arylation of Oxalates Derived from α-Hydroxy Esters with Aryl Halides

  摘要：

  A Ni-catalyzed reductive cross-coupling of alpha-hydroxycarbonyl compounds modified with oxalyl groups and aryl halides has been developed that furnishes alpha-aryl esters under mild conditions and tolerates a variety of functionalized aryl halides bearing electron withdrawing and-donating groups. This work highlights C-O bond fragmentation on secondary alkyl carbon centers that generates alpha-carbonyl radicals.

  DOI：

  10.1021/acs.orglett.9b00174
• 作为产物：
  描述：

  甲基戊酰氯 、 乳酸甲酯 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以80%的产率得到Methyl 2-<(methoxallyl)oxy>acetate
  参考文献：
  名称：

  α-羟基羰基化合物草酸盐与溴乙烯的镍催化还原交叉偶联反应

  摘要：

  公开了一种镍催化的交叉亲电偶联物，其中使用了一系列溴乙烯作为亲电试剂，其中衍生自 α-羟基羰基的草酸盐作为羰基自由基偶联配偶体的前体。该方法与广泛的官能团兼容，为构建 β,γ-不饱和羰基化合物提供了补充解决方案。

  DOI：

  10.1055/s-0040-1719881

文献信息

• Reaction of Superoxide with Ascorbic Acid Derivatives: Insight into the Superoxide-Mediated Oxidation of Dehydroascorbic Acid
  作者：Aryeh A. Frimer、Pessia Gilinsky-Sharon

  DOI：10.1021/jo00114a031

  日期：1995.5

  In order to gain greater insight into the mechanism of superoxide-mediated oxidation of ascorbic acid (1) in aprotic media, we reacted O-2(.-) (generated from KO2/18-crown-6 in toluene) with vitamin C derivatives 13a and 14a and the corresponding mono- and dimethoxy analogs 13b and 13c, respectively. Dihydroxyfuranones 13a and 14a underwent oxidative cleavage with O-2(.-) yielding, upon methyl iodide workup, the corresponding keto ester (15 or 17, respectively) and threonic acid analog (16 or 18, respectively). On the other hand, mono- and dimethoxy analogs 13b and 13c each react with superoxide to give a single isolable product, oxyester 16 and alkylidenefuranone 20, respectively. Finally, 13a reacts with tert-butoxide, again yielding 16 as the major product. The data are best resolved by suggesting that ascorbic acid analogs 13a and 14a (and presumably ascorbic acid as well) are oxidized by O-2(.-) to the corresponding triketone 21 which reacts in turn by attack at the highly electrophilic central carbonyl C-2. Cyclization of the resulting 2-peroxy 1,3-diketone 22 into the C-1 carbonyl, followed by oxidative cleavage, saponification, and methylation, yields the observed products. By contrast, O-2(.-) oxidation of 13b and tert-butoxide oxidation of 13a yield 3-peroxy-1,2-diketone 29 which cyclizes into the C-1 carbonyl ultimately yielding 16. Finally, 13c, which lacks enolic hydrogens, undergoes abstraction of the gamma-hydrogen followed by the elimination of acetone, yielding 20. Similarly, 5,6-dihydropyrone 33 undergoes superoxide-mediated elimination yielding dienone 34. The data presented herein are consistent with the mechanism suggested by Sawyer et al. (J. Am. Chem. Sec. 1982, 104, 6273-6278) for the superoxide-mediated oxidation of dehydroascorbic acid (2)-with the modification that the position of initial O-2(.-) attack is at the C-2 (rather than the C-3) carbonyl.
• Photooxygenation of ascorbic acid derivatives and model compounds
  作者：Byoung Mog Kwon、Christopher S. Foote、Saeed I. Khan

  DOI：10.1021/ja00187a047

  日期：1989.3
• Ni-Catalyzed Reductive C–O Bond Arylation of Oxalates Derived from α-Hydroxy Esters with Aryl Halides
  作者：Mengyu Gao、Deli Sun、Hegui Gong

  DOI：10.1021/acs.orglett.9b00174

  日期：2019.3.15

  A Ni-catalyzed reductive cross-coupling of alpha-hydroxycarbonyl compounds modified with oxalyl groups and aryl halides has been developed that furnishes alpha-aryl esters under mild conditions and tolerates a variety of functionalized aryl halides bearing electron withdrawing and-donating groups. This work highlights C-O bond fragmentation on secondary alkyl carbon centers that generates alpha-carbonyl radicals.
• Nickel-Catalyzed Reductive Cross-Coupling of Oxalates Derived from α-Hydroxy Carbonyls with Vinyl Bromides
  作者：Fan Wu、Cheng Ye、Weiqi Tong

  DOI：10.1055/s-0040-1719881

  日期：2022.5

  A nickel-catalyzed cross-electrophile coupling is disclosed in which a range of vinyl bromides were utilized as electrophiles with oxalates derived from α-hydroxy carbonyls as precursors to carbonyl radical coupling partners. This method is compatible with a broad range of functional groups, providing a complementary solution for the construction of β,γ-unsaturated carbonyl compounds.

  公开了一种镍催化的交叉亲电偶联物，其中使用了一系列溴乙烯作为亲电试剂，其中衍生自 α-羟基羰基的草酸盐作为羰基自由基偶联配偶体的前体。该方法与广泛的官能团兼容，为构建 β,γ-不饱和羰基化合物提供了补充解决方案。