(Z)-2-Formyl-1-<(4-methoxyphenyl)methylene>-1,2,3,4,5,6,7,8-octahydroisoquinoline | 116172-20-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (Z)-2-Formyl-1-<(4-methoxyphenyl)methylene>-1,2,3,4,5,6,7,8-octahydroisoquinoline
• 英文别名: (Z)-N-formyl-1-(4-methoxyphenylmethylene)-3,4,5,6,7,8-hexahydroisoquinoline；(1Z)-1-[(4-methoxyphenyl)methylidene]-3,4,5,6,7,8-hexahydroisoquinoline-2-carbaldehyde
• CAS: 116172-20-4
• 化学式: C₁₈H₂₁NO₂
• 分子量: 283.37
• InChiKey: FJHQLTDBSGWURB-PDGQHHTCSA-N

物化性质

• 沸点：
  507.3±50.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.39
• 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：

  (Z)-2-Formyl-1-<(4-methoxyphenyl)methylene>-1,2,3,4,5,6,7,8-octahydroisoquinoline 在 Ru(OCOCF₃)2((S)-tolbinap) 氢气 作用下， 以 甲醇 为溶剂， 30.0 ℃ 、10.13 MPa 条件下， 反应 100.0h， 生成 右美沙芬
  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：

  N-[2-(1,1-环己烯基)-乙基]-4-甲氧基苯基乙酰胺 在 三氯氧磷 作用下， 以 四氢呋喃 、 吡啶 、 苯 为溶剂， 反应 8.0h， 生成 (Z)-2-Formyl-1-<(4-methoxyphenyl)methylene>-1,2,3,4,5,6,7,8-octahydroisoquinoline
  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

文献信息

• Ruthenium-phosphine complex
  申请人：Takasago International Corporation

  公开号：US04954644A1

  公开（公告）日：1990-09-04

  A ruthenium-phosphine complex is disclosed, which is represented by formula (I): [Ru(R-BINAP)MCl.sub.k ].sub.l X.sub.m (I) wherein R-BINAP represents a tertiary phosphine represented by formula (II): ##STR1## wherein R represents hydrogen atom or methyl group; M represents Zn, Al, Ti, or Sn; X represents N(C.sub.2 H.sub.5).sub.3 or CH.sub.3 CO.sub.2 ; in the case that X represents N(C.sub.2 H.sub.5).sub.3, l is 2 and m is 1, and when M represents Zn, then k is 4, when M represents Al, then k is 5, and when M represents Ti or Sn, then k is 6; and in the case that X represents CH.sub.3 CO.sub.2, l is 1 and m is 2, and when M represents Zn, then k is 2, when M represents Al, then k is 3, and when M represents Ti or Sn, then k is 4.

  本发明公开了一种钌-膦配合物，其由式(I)表示：[Ru(R-BINAP)MCl.sub.k ].sub.l X.sub.m (I)其中，R-BINAP表示由式(II)表示的三级膦：##STR1##其中，R表示氢原子或甲基基团；M表示Zn、Al、Ti或Sn；X表示N(C.sub.2 H.sub.5).sub.3或CH.sub.3 CO.sub.2；当X表示N(C.sub.2 H.sub.5).sub.3时，l为2，m为1，当M表示Zn时，k为4，当M表示Al时，k为5，当M表示Ti或Sn时，k为6；当X表示CH.sub.3 CO.sub.2时，l为1，m为2，当M表示Zn时，k为2，当M表示Al时，k为3，当M表示Ti或Sn时，k为4。
• 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.
• New efficient methods for the synthesis and in-situ preparation of ruthenium(II) complexes of atropisomeric diphosphines and their application in asymmetric catalytic hydrogenations
  作者：Bernd Heiser、Emil A. Broger、Yvo Crameri

  DOI：10.1016/s0957-4166(00)82157-6

  日期：1991.1

  A new synthetically useful method for the synthesis of the diphosphine ruthenium dicarboxylato complexes (P-P)Ru(O2CR)2 (R = CF3 and CH3) is presented, which uses the easily accessible complex (COD)2Ru2(mu-O2CCF3)4 as starting material. This complex as well as (COD)Ru(eta-2-O2CCH3)2 and (COD)2Ru2Cl4(NCCH3) have been shown to be suitable precursor complexes for the in-situ preparation of ruthenium(II) dicarboxylato and dichloro complexes of atropisomeric diphosphines, respectively. The high efficacy of the preformed and in-situ generated ruthenium complexes as precatalysts is demonstrated in asymmetric hydrogenations of allylic alcohols, enamides, and a beta-keto ester.
• KITAMURA, M.;HSIAO, YI;NOYORI, R.;TAKAYA, H., TETRAHEDRON LETT., 28,(1987) N 41, 4829-4832
  作者：KITAMURA, M.、HSIAO, YI、NOYORI, R.、TAKAYA, H.

  DOI：——

  日期：——
• Ruthenium-phosphine complexes useful as catalysts
  申请人：Takasago International Corporation

  公开号：EP0307168B1

  公开（公告）日：1993-03-10