methyl 4-(methoxymethoxy)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-benzodioxole-5-carboxylate | 1035055-67-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: methyl 4-(methoxymethoxy)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-benzodioxole-5-carboxylate
• CAS: 1035055-67-4
• 化学式: C₁₇H₂₃BO₈
• 分子量: 366.176
• InChiKey: VUCYQBIDBGBLJG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.48
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  81.7
• 氢给体数：
  0
• 氢受体数：
  8

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 、 methyl 4-(methoxymethoxy)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-benzodioxole-5-carboxylate 以63%的产率得到(2R,4R,3S,4aS)-2,3,4,7-tetra(methoxymethoxy)-3,4,4a,5-tetrahydro-2H-1,3-dioxolo[4,5-j]phenanthridin-6-one
  参考文献：
  名称：

  恩卡西碱，恩可可啶和某些对映体相关同源物的生物学评估。

  摘要：

  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。

  DOI：

  10.1002/cbdv.200800319
• 作为产物：
  描述：

  methyl 6-iodo-4-(methoxymethoxy)-1,3-benzodioxole-5-carboxylate 、 频那醇硼烷 在 palladium diacetate 三乙胺 、 2-(二环己基膦基)联苯 作用下， 以 1,4-二氧六环 为溶剂， 反应 1.33h， 以54%的产率得到methyl 4-(methoxymethoxy)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-benzodioxole-5-carboxylate
  参考文献：
  名称：

  A chemoenzymatic total synthesis of ent-narciclasine

  摘要：

  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.

  DOI：

  10.1016/j.tet.2008.01.113

文献信息

• 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.
• 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。