(E)-1,3-butadien-1-yl N,N-dimethylcarbamate | 142891-87-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (E)-1,3-butadien-1-yl N,N-dimethylcarbamate
• 英文别名: [(1E)-buta-1,3-dienyl] N,N-dimethylcarbamate
• CAS: 142891-87-0
• 化学式: C₇H₁₁NO₂
• 分子量: 141.17
• InChiKey: BDBLLOQQLZYFQM-AATRIKPKSA-N

物化性质

• 沸点：
  196.5±13.0 °C(Predicted)
• 密度：
  0.983±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-甲基丙烯醛 、 (E)-1,3-butadien-1-yl N,N-dimethylcarbamate 在 (R)-BINOL-derived titanium complex 1a (X=Cl) 、 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 58.0h， 生成 (1S,2R)-2-<(N,N-dimethylcarbamoyl)oxy>-1-methyl-3-cyclohexenecarbaldehyde 、 (1S,2R)-2-<(N,N-dimethylcarbamoyl)oxy>-1-methyl-3-cyclohexenecarbaldehyde
  参考文献：
  名称：

  Chiral titanium complex-catalyzed Diels-Alder reaction: A practical route to anthracycline intermediates

  摘要：

  Asymmetric Diels-Alder reactions of methacrolein and 1,4-naphthoquinone with 1,3-dienol derivatives catalyzed by the chiral binaphthol (BINOL)-derived titanium complex 1 are shown to provide the corresponding endo-adducts in high enantiomeric purity. The naphthoquinone adduct can serve as a synthetic intermediate of tetracycline antibiotics.

  DOI：

  10.1016/s0957-4166(00)86118-2
• 作为产物：
  描述：

  二甲氨基甲酰氯 、 丁烯-2-醛 在 potassium tert-butylate 作用下， 生成 (E)-1,3-butadien-1-yl N,N-dimethylcarbamate
  参考文献：
  名称：

  Asymmetric Catalysis of Diels-Alder Cycloadditions by an MS-Free Binaphthol-Titanium Complex: Dramatic Effect of MS, Linear vs Positive Nonlinear Relationship, and Synthetic Applications

  摘要：

  Asymmetric Diels-Alder (D.-A.) reaction of 5-hydroxynaphthoquinone (juglone) with butadienyl acetate catalyzed by the binaphthol-derived chiral titanium (BINOL-Ti) complex 1 proceeds in only 9% ee in the presence of molecular sieves (MS). Remarkably, however, this reaction proceeds in 76-96% ee with BINOL-Ti complex 1 freed from MS to provide the endo-adducts useful for the synthesis of anthracyclines and tetracyclines. The solid MS-free BINOL-Ti complex 1 is stable for months at -20 degrees C, Enhancements in endo selectivity and asymmetric induction are observed with the MS-free BINOL-Ti 1 also in the catalyzed D.-A. cycloaddition of methacrolein and glyoxylate with 1,3-dienol ethers and esters. The glyoxylate adducts can be converted to the mevinolin (compactin) intermediates. Surprisingly, the MS-free complex 1 exhibits not only a linear relationship between the ee's of BINOL-Ti 1 and the D.-A. products but also a positive nonlinear effect (asymmetric amplification), depending simply on the mixing manner of (R)-1 with (S)-1 or (+/-)-1.

  DOI：

  10.1021/ja00086a014

文献信息

• US5155240A
  申请人：——

  公开号：US5155240A

  公开（公告）日：1992-10-13
• Asymmetric Catalysis of Diels-Alder Cycloadditions by an MS-Free Binaphthol-Titanium Complex: Dramatic Effect of MS, Linear vs Positive Nonlinear Relationship, and Synthetic Applications
  作者：Koichi Mikami、Yukihiro Motoyama、Masahiro Terada

  DOI：10.1021/ja00086a014

  日期：1994.4

  Asymmetric Diels-Alder (D.-A.) reaction of 5-hydroxynaphthoquinone (juglone) with butadienyl acetate catalyzed by the binaphthol-derived chiral titanium (BINOL-Ti) complex 1 proceeds in only 9% ee in the presence of molecular sieves (MS). Remarkably, however, this reaction proceeds in 76-96% ee with BINOL-Ti complex 1 freed from MS to provide the endo-adducts useful for the synthesis of anthracyclines and tetracyclines. The solid MS-free BINOL-Ti complex 1 is stable for months at -20 degrees C, Enhancements in endo selectivity and asymmetric induction are observed with the MS-free BINOL-Ti 1 also in the catalyzed D.-A. cycloaddition of methacrolein and glyoxylate with 1,3-dienol ethers and esters. The glyoxylate adducts can be converted to the mevinolin (compactin) intermediates. Surprisingly, the MS-free complex 1 exhibits not only a linear relationship between the ee's of BINOL-Ti 1 and the D.-A. products but also a positive nonlinear effect (asymmetric amplification), depending simply on the mixing manner of (R)-1 with (S)-1 or (+/-)-1.
• Chiral titanium complex-catalyzed Diels-Alder reaction: A practical route to anthracycline intermediates
  作者：Koichi Mikami、Masahiro Terada、Yukihiro Motoyama、Takeshi Nakai

  DOI：10.1016/s0957-4166(00)86118-2

  日期：1991.1

  Asymmetric Diels-Alder reactions of methacrolein and 1,4-naphthoquinone with 1,3-dienol derivatives catalyzed by the chiral binaphthol (BINOL)-derived titanium complex 1 are shown to provide the corresponding endo-adducts in high enantiomeric purity. The naphthoquinone adduct can serve as a synthetic intermediate of tetracycline antibiotics.