(R)-2-Formyl-1-<(4-methoxyphenyl)methyl>-1,2,3,4,5,6,7,8-octahydroispquinoline | 51773-23-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 英文名称: (R)-2-Formyl-1-<(4-methoxyphenyl)methyl>-1,2,3,4,5,6,7,8-octahydroispquinoline
• 英文别名: (R)-1-(4-Methoxybenzyl)-3,4,5,6,7,8-hexahydroisoquinoline-2(1H)-carbaldehyde；(1R)-1-[(4-methoxyphenyl)methyl]-3,4,5,6,7,8-hexahydro-1H-isoquinoline-2-carbaldehyde
• CAS: 51773-23-0
• 化学式: C₁₈H₂₃NO₂
• 分子量: 285.386
• InChiKey: XSOPBBOEINVWML-GOSISDBHSA-N

物化性质

• 沸点：
  466.8±38.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)
• 溶解度：
  氯仿（少量溶解）、DMSO（少量溶解）、乙酸乙酯（少量溶解）、甲醇（少量溶解）

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1-(4-甲氧基苄基)-3,4,5,6,7,8,-六氢异喹啉 在 Ru(CF3COO)2<(R)-TolBINAP> 吡啶 、 氢气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 30.0 ℃ 、10.13 MPa 条件下， 反应 172.0h， 生成 (R)-2-Formyl-1-<(4-methoxyphenyl)methyl>-1,2,3,4,5,6,7,8-octahydroispquinoline
  参考文献：
  名称：

  General asymmetric synthesis of isoquinoline alkaloids. Enantioselective hydrogenation of enamides catalyzed by BINAP-ruthenium(II) complexes

  摘要：

  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.

  DOI：

  10.1021/jo00081a007

文献信息

• 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：——