(Z)-1-Formyl-2-<(4-methoxyphenyl)methylene>-3,4-dimethyl-1,2,5,6-tetrahydropyridine | 116172-10-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (Z)-1-Formyl-2-<(4-methoxyphenyl)methylene>-3,4-dimethyl-1,2,5,6-tetrahydropyridine
• 英文别名: (Z)-1-Formyl-2-[(4-methoxyphenyl)methylene]-3,4-dimethyl-1,2,5,6-tetrahydropyridine；(6Z)-6-[(4-methoxyphenyl)methylidene]-4,5-dimethyl-2,3-dihydropyridine-1-carbaldehyde
• CAS: 116172-10-2
• 化学式: C₁₆H₁₉NO₂
• 分子量: 257.332
• InChiKey: QFXFXXNZQLAYOO-YBEGLDIGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.23
• 重原子数：
  19.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  29.54
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (Z)-1-Formyl-2-<(4-methoxyphenyl)methylene>-3,4-dimethyl-1,2,5,6-tetrahydropyridine 在 Ru(OCOCF₃)2((R)-tolbinap) 氢气 作用下， 以 甲醇 为溶剂， 25.0 ℃ 、10.13 MPa 条件下， 反应 120.0h， 以98%的产率得到(R)-1-Formyl-2-<(4-methoxyphenyl)methyl>-3,4-dimethyl-1,2,5,6-tetrahydropyridine
  参考文献：
  名称：

  General asymmetric synthesis of benzomorphans and morphinans via enantioselective hydrogenation

  摘要：

  DOI：

  10.1016/s0040-4039(00)96636-x
• 作为产物：
  描述：

  2-<(4-Methoxyphenyl)methylene>-3,4-dimethyl-5,6-dihydropyridine hydrochloride 生成 (Z)-1-Formyl-2-<(4-methoxyphenyl)methylene>-3,4-dimethyl-1,2,5,6-tetrahydropyridine
  参考文献：
  名称：

  KITAMURA, M.;HSIAO, YI;NOYORI, R.;TAKAYA, H., TETRAHEDRON LETT., 28,(1987) N 41, 4829-4832

  摘要：

  DOI：

文献信息

• General asymmetric synthesis of isoquinoline alkaloids. Enantioselective hydrogenation of enamides catalyzed by BINAP-ruthenium(II) complexes
  作者：Masato Kitamura、Yi Hsiao、Masako Ohta、Masaki Tsukamoto、Tetsuo Ohta、Hidemasa Takaya、Ryoji Noyori

  DOI：10.1021/jo00081a007

  日期：1994.1

  In the presence of a small amount of RuX(2)[(R)- or (S)-BINAP] (X = anionic ligand) a wide range of (Z)-2-acyl-1-benzylidene-1,2,3,4-tetrahydroisoquinolines are hydrogenated to give the saturated products in nearly quantitative yields and in high (up to 100 %) optical yields. The enamide substrates are selectively prepared by N-acylation of the corresponding 1-benzylated 3,4-dihydroisoquinolines under suitable acylation conditions; some crystalline materials having low solubility are obtained by a second-order Z/E stereomutation technique utilizing the double-bond photolability and lattice energy effects. This asymmetric hydrogenation sets the key stereogenic center in a predictable manner, either R or S flexibly, at the C(1) position of the benzylated tetrahydroisoquinolines. The chiral products are converted by standard functional group modification to tetrahydropapaverine, laudanosine, tretoquinol, norreticuline, etc. Hydrogenation of the simple 1-methylene substrate is used fbr synthesis of salsolidine. This enantioselective hydrogenation is applied to the synthesis of morphine and its artificial analogues such as morphinans and benzomorphans of either chirality. A mnemonic device is presented for predicting the reactivity and enantiofacial selection of the BINAP-Ru catalyzed hydrogenation. Reaction with BINAP-Rh catalyst proceeds with a lower enantioselectivity and an opposite sense of asymmetric induction.