[(1R,4S,5R,7S)-4-羟基-8-氮杂双环[3.2.1]辛烷-7-基]乙酸酯 | 74239-84-2

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 托烷生物碱
• 中文名称: [(1R,4S,5R,7S)-4-羟基-8-氮杂双环[3.2.1]辛烷-7-基]乙酸酯
• 中文别名: 4-氯-N-甲基-6-(4-甲基哌嗪-1-基)-5-(甲基硫烷基)嘧啶-2-胺；包公藤甲素
• 英文名称: (-)-Bao Gong Teng A
• 英文别名: Bao gong teng A；[(1R,2S,5R,6S)-2-hydroxy-8-azabicyclo[3.2.1]octan-6-yl] acetate
• CAS: 74239-84-2
• 化学式: C₉H₁₅NO₃
• 分子量: 185.223
• InChiKey: FSXBMHMVOFJROW-HXFLIBJXSA-N

物化性质

• 熔点：
  76-78 °C
• 沸点：
  302.2±32.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  58.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  tert-butyl (2R,3S)-3-hydroxy-2-(3-tert-butyldimethylsilyloxypropyl)-5-oxopyrrolidine-1-carboxylate 在 2,6-二甲基吡啶 、 sodium tetrahydroborate 、 samarium diiodide 、 三氟甲磺酸三甲基硅酯 、 三氟化硼乙醚 、 戴斯-马丁氧化剂 、 lithium tri-t-butoxyaluminum hydride 、 叔丁醇 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 11.5h， 生成 [(1R,4S,5R,7S)-4-羟基-8-氮杂双环[3.2.1]辛烷-7-基]乙酸酯
  参考文献：
  名称：

  一种构造羟基化的托烷骨架的新方法：（-）-Bao Gong Teng A的对映选择性合成。

  摘要：

  描述了一种高效且高度非对映选择性的方法，用于构建羟基化的托烷骨架。该方法的特点是由BF（3）.OEt（2）和SmI（2）协同介导的N-酰基N，O-乙缩醛与醛的新分子内还原偶联反应。在此方法的基础上，完成了对-（Bao-Bong Teng A）的新对映选择性全合成。

  DOI：

  10.1039/c0cc04371k

文献信息

• Methyl (S)-Lactate as a Chiral Auxiliary in the Asymmetric Synthesis of Bao Gong Teng A
  作者：Vinh C. Pham、James L. Charlton

  DOI：10.1021/jo00129a053

  日期：1995.12

  The asymmetric synthesis of Bao Gong Teng A, (-)-1, a natural product that shows strong antiglaucoma properties, is described. The synthesis begins with an asymmetric 1,3-dipolar cycloaddition of the acrylate of methyl (S)-lactate to the betaine of N-benzyl-3-hydroxypyridinium chloride giving cycloadduct 59 as a major product. The crude cycloadduct was reduced by catalytic hydrogenation to produce 6 in 61% yield. The ketone 6 was reduced with LiAl(OtBu)(3)H to give exo alcohol 7b in 62% yield. Protection of the alcohol group followed by replacement of the benzyl group on the nitrogen with a Boc group gave 12, which was then hydrolyzed to the acid 13 in 91% yield for the three steps. The acid 13 was converted to the ketone 14 in 82% yield via the acid chloride. Baeyer-Villiger oxidation converted 14 to 15 in 52% yield. Optically pure Bao Gong Teng A was obtained in 9% overall yield by the removal of both the Boc and the TBDMS groups using 1% HCl-EtOH.
• Organometallic Enantiomeric Scaffolding:  Organometallic Chirons. Total Synthesis of (−)-Bao Gong Teng A by a Molybdenum-Mediated [5+2] Cycloaddition
  作者：Yongqiang Zhang、Lanny S. Liebeskind

  DOI：10.1021/ja055623x

  日期：2006.1.1

  Bao Gong Teng A, an optically active tropane alkaloid with hypotensive and miotic activity isolated from the Chinese herb Erycibe obtusifolia Benth, was synthesized by an "organometallic Chiron" strategy in which single enantiomers of TpMo(CO)(2)(eta(3)-pyriclinyl) complexes are produced in quantity and then elaborated easily and efficiently to generate, after demetalation, highly enantiopure advanced synthetic intermediates possessing the tropane core.