(S)-2,3,9,10,11-pentamethoxyhomoprotoberberine | 111623-26-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯氮卓类
• 英文名称: (S)-2,3,9,10,11-pentamethoxyhomoprotoberberine
• 英文别名: (S)-2,3,9,10,11-pentamethoxy-5,6,8,13,14,14a-hexahydrobenzo[5,6]azepino[2,1-a]isoquinoline；(11S)-4,5,6,14,15-pentamethoxy-1-azatetracyclo[9.8.0.03,8.012,17]nonadeca-3,5,7,12,14,16-hexaene
• CAS: 111623-26-8
• 化学式: C₂₃H₂₉NO₅
• 分子量: 399.487
• InChiKey: MTVWALWAOHLQQW-SFHVURJKSA-N

物化性质

• 熔点：
  228-229 °C
• 沸点：
  534.5±50.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  49.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  methyl <(2S,3R)-dihydroxy-3-(6',7'-dimethoxy-1',2',3',4'-tetrahydroisoquinolin-1'(R)-yl)>propanoate hydrochloride 在 platinum(IV) oxide 吡啶 、 甲醇 、 sodium periodate 、 正丁基锂 、 氢溴酸 、 甲基锂 、 氢气 、 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 水 为溶剂， -30.0~25.0 ℃ 、101.33 kPa 条件下， 反应 14.25h， 生成 (S)-2,3,9,10,11-pentamethoxyhomoprotoberberine
  参考文献：
  名称：

  异喹啉生物碱的对映选择性合成：苯乙基异喹啉和阿朴啡生物碱

  摘要：

  从 D-(-)-酒石酸开始，开发了一种新的改进方法，用于制备 (R)-2-alkoxycarbonyl-1-formyl-1,2,3,4-四氢-6,7-二甲氧基异喹啉。这些醛在高对映体纯度的异喹啉生物碱的不对称合成中的用途已扩展到苯乙基异喹啉的合成，后者已通过直接步骤进一步转化为高原小檗碱和高卟啉环系统。以这种方式，已经合成了 (S)-高莫拉丹苷、(S)-5'-甲氧基高莫拉丹苷、(S)-2,3,9,10,11-五甲氧基高原小檗碱和 (S)-O-methylkreysigine。(S)-laudanosine 转化为 (S)-glaucine，一种阿朴啡生物碱，也已实现。

  DOI：

  10.1139/v87-393

文献信息

• Asymmetric synthesis of six tetrahydroisoquinoline natural products through α-amination of an aldehyde
  作者：Anas Ansari、Amol B. Gorde、Ramesh Ramapanicker

  DOI：10.1016/j.tet.2021.132121

  日期：2021.5

  An enantioselective route towards the synthesis of C-1 substituted tetrahydroisoquinoline natural products is reported. Six different natural products are synthesized from a single aldehyde using proline-catalyzed asymmetric α-hydrazination reaction as the key step. The highly enantioselective introduction of an amino group is exploited to synthesize (−)-calycotomine, (−)-salsolidine, (−)-carnegine

  报道了合成C-1取代的四氢异喹啉天然产物的对映选择性途径。以脯氨酸催化的不对称α-酰化反应为关键步骤，由单一醛合成六种不同的天然产物。利用氨基的高度对映选择性引入来合成（-）-花椰菜碱，（-）-沙丁胺碱，（-）-肉碱，（+）-高麦芽糖苷，（+）-高原小ber碱和（+）-crispineA。
• The Synthesis of Isoquinoline Alkaloid and Its Related Compounds Using Alanine Derivatives as Chiral Auxiliaries
  作者：Takashi Itoh、Kazuhiro Nagata、Masashi Yokoya、Michiko Miyazaki、Keiko Kameoka、Shigeru Nakamura、Akio Ohsawa

  DOI：10.1248/cpb.51.951

  日期：——

  Chiral 1-substituted isoquinoline derivatives, which were obtained by the reaction using alanine derivatives as chiral auxiliaries, were transformed to (S)-2,3,9,10,11-pentamethoxyhomoprotoberberine (7) and a synthetic intermediate for O-methylkreysigine (9) in good yields and high stereoselectivity. The corresponding chiral allyl derivative of isoquinoline was transformed to a pyrrolidinoisoquinoline

  通过使用丙氨酸衍生物作为手性助剂的反应获得的手性1-取代的异喹啉衍生物被转化为（S）-2,3,9,10,11-五甲氧基高原型小ine碱（7）和O-甲基克雷西金的合成中间体（ 9）产率高且立体选择性高。异喹啉的相应手性烯丙基衍生物以高度对映选择性的方式转化为吡咯烷基异喹啉（16）。
• Enantioselective Synthesis of Some Tetracyclic Isoquinoline Alkaloids by Asymmetric Transfer Hydrogenation Catalysed by a Chiral Ruthenium Complex
  作者：Joanna Szawkało、Zbigniew Czarnocki

  DOI：10.1007/s00706-005-0341-8

  日期：2005.9

  Asymmetric transfer hydrogenation catalysed by chiral ruthenium complexes was the method for enantioselective synthesis of ( R )-(+)-coralydine, ( S )-(−)-homoprotoberberine, and ( S )-(+)-homoaporphine in fair to excellent enantiomeric purity.

  手性钌配合物催化的不对称转移氢化反应是对映体选择性合成（ R ）-（+）-可乐树碱，（ S ）-（-）-高原型小ber碱和（ S ）-（+）-高磷吗啡碱的对映体纯度。
• Highly Enantioselective Catalytic Cross-Dehydrogenative Coupling of <i>N</i>-Carbamoyl Tetrahydroisoquinolines and Terminal Alkynes
  作者：Shutao Sun、Chengkun Li、Paul E. Floreancig、Hongxiang Lou、Lei Liu

  DOI：10.1021/acs.orglett.5b00447

  日期：2015.4.3

  The first catalytic asymmetric cross-dehydrogenative coupling of cyclic carbamates and terminal alkynes has been established. The reaction features high enantiocontrol and excellent functional group tolerance and displays a wide range of structurally and electronically diverse carbamates as well as terminal alkynes. N-Acyl hemiaminals were identified as the reactive intermediates through preliminary control experiments. Employing readily removable carbamates as substrates rather than traditionally adopted N-aryl amines allows applications in complex molecule synthesis and therefore advances the CH functionalization strategy to a synthetically useful level.
• Nagata, Kazuhiro; Itoh, Takashi; Kameoka, Keiko, Heterocycles, 2001, vol. 55, # 12, p. 2269 - 2272
  作者：Nagata, Kazuhiro、Itoh, Takashi、Kameoka, Keiko、Miyazaki, Michiko、Ohsawa, Akio

  DOI：——

  日期：——