(1R,4R,5S,6R)-2-bromo-4,5,6-tris(methoxymethoxy)-cyclohex-2-enamine | 951345-92-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,4R,5S,6R)-2-bromo-4,5,6-tris(methoxymethoxy)-cyclohex-2-enamine
• 英文别名: (1R,4R,5S,6R)-2-bromo-4,5,6-tris(methoxymethoxy)cyclohex-2-en-1-amine
• CAS: 951345-92-9
• 化学式: C₁₂H₂₂BrNO₆
• 分子量: 356.214
• InChiKey: DPAUWODEOCFPJT-NOOOWODRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  20
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  81.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (1R,4R,5S,6R)-2-bromo-4,5,6-tris(methoxymethoxy)-cyclohex-2-enamine 在 palladium diacetate 三甲基溴硅烷 、 四丁基溴化铵 、 potassium carbonate 作用下， 以 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 4.0h， 生成 (+/-)-lycoricidine
  参考文献：
  名称：

  Chemoenzymatic Approaches to Lycorine-Type Amaryllidaceae Alkaloids:  Total Syntheses of ent-Lycoricidine, 3-epi-ent-Lycoricidine, and 4-Deoxy-3-epi-ent-lycoricidine

  摘要：

  The readily available and enzymatically derived cis-1,2-dihydrocatechol 4 has been elaborated, over 11 steps including an Overman rearrangement, into the non-natural enantiomer, (-)-1, of the alkaloid lycoricidine [(+)-1]. Related chemistries have provided analogues 18, 19, and 26.

  DOI：

  10.1021/ol701552r
• 作为产物：
  描述：

  (3aS,4R,5R,7aS)-7-bromo-4,5-bis(methoxymethoxy)-2-(4-methoxyphenyl)-3a,4,5,7a-tetrahydrobenzo[d][1,3]dioxole 在 水 、 sodium hydride 、 二异丁基氢化铝 、 potassium carbonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 二氯甲烷 、 邻二氯苯 、 甲苯 为溶剂， 反应 38.25h， 生成 (1R,4R,5S,6R)-2-bromo-4,5,6-tris(methoxymethoxy)-cyclohex-2-enamine
  参考文献：
  名称：

  Chemoenzymatic Approaches to Lycorine-Type Amaryllidaceae Alkaloids:  Total Syntheses of ent-Lycoricidine, 3-epi-ent-Lycoricidine, and 4-Deoxy-3-epi-ent-lycoricidine

  摘要：

  The readily available and enzymatically derived cis-1,2-dihydrocatechol 4 has been elaborated, over 11 steps including an Overman rearrangement, into the non-natural enantiomer, (-)-1, of the alkaloid lycoricidine [(+)-1]. Related chemistries have provided analogues 18, 19, and 26.

  DOI：

  10.1021/ol701552r

文献信息

• Biological Evaluation of<i>ent</i>-Narciclasine,<i>ent</i>-Lycoricidine, and Certain Enantiomerically-Related Congeners
  作者：Maria Matveenko、Martin G. Banwell、Max Joffe、Soosan Wan、Emmanuelle Fantino

  DOI：10.1002/cbdv.200800319

  日期：2009.5

  The non-natural enantiomeric forms of narciclasine and lycoricidine ((-)-1 and (-)-2, respectively), as well as congeners 3-6 are available through chemoenzymatic synthesis. Accordingly, they have now been tested for their cytotoxic effects in a 13-member human cancer cell-line panel and found to be only weakly active. In contrast, an authentic sample of the natural enantiomeric form of narciclasine

  可以通过化学酶促合成获得水杨酸和二十二碳四烯酸（分别为（-）-1和（-）-2）以及同类物3-6的非天然对映体形式。因此，现在已经在13人的人类癌细胞系中测试了它们的细胞毒性作用，发现它们的活性很弱。相反，发现天然的对映体形式的水仙子碱（（+）-1）的真实样品在同一屏幕中具有很高的活性。
• A chemoenzymatic total synthesis of ent-narciclasine
  作者：Maria Matveenko、Martin G. Banwell、Anthony C. Willis

  DOI：10.1016/j.tet.2008.01.113

  日期：2008.5

  The synthesis of the title compound [(-)-1] has been achieved, for the first time, by reacting the aryl boronic acid ester 4 with the amino-conduritol derivative 6 under Suzuki-Miyaura cross-coupling conditions then subjecting the product phenanthridinone 23 to a global deprotection process using trimethylsilyl bromide. The aromatic building block 4 was prepared in ten steps from piperonal while compound 6 was obtained in nine steps from the enantiomerically pure cis-1,2-dihydrocatechol 7. This last compound is available, in multi-gram quantities, through a whole-cell-mediated biotransformation of bromobenzene using genetically engineered organisms that over-express the responsible enzyme, namely toluene dioxygenase. Since the enantiomer of compound 7 is available by related means, the present work also represents a formal total synthesis of the alkaloid narciclasine [(+)-1]. The single-crystal X-ray analysis of compound 13 is reported. (C) 2008 Elsevier Ltd. All rights reserved.