methyl 6-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzo[d][1,3]dioxole-5-carboxylate | 1175589-03-3

• 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 6-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzo[d][1,3]dioxole-5-carboxylate
• 英文别名: Methyl 6-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1,3-benzodioxole-5-carboxylate
• CAS: 1175589-03-3
• 化学式: C₁₄H₁₇BO₆
• 分子量: 292.096
• InChiKey: ZOHOBUKEWBMMAC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.97
• 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：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 6-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzo[d][1,3]dioxole-5-carboxylate 在 吡啶 、 1,1'-双(二苯膦基)二茂铁二氯化钯(II)二氯甲烷复合物 、 草酰氯 、 氢气 、 溶剂黄146 、 sodium hydroxide 、 silver(l) oxide 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙腈 为溶剂， -78.0~50.0 ℃ 、6.0 MPa 条件下， 反应 14.35h， 生成 methylsulfanylmethyl 6-[(3R,5S)-5-methoxy-3-[2-[methyl(prop-2-enoxycarbonyl)amino]ethyl]-6-oxocyclohexen-1-yl]-1,3-benzodioxole-5-carboxylate
  参考文献：
  名称：

  化学酶的全合成金缕梅生物碱narseronine

  摘要：

  使用对映体纯的和酶衍生的顺式-1,2-二氢邻苯二酚2作为起始原料，完成了标题生物碱1的15步完全立体控制的总合成。最终的关键步骤涉及将仲胺16分子内杂化-迈克尔加成至束缚的烯酮部分，然后通过其与相邻酯残基的反应捕获所得烯醇化物。

  DOI：

  10.1016/j.tetlet.2011.06.050
• 作为产物：
  描述：

  甲基-6-溴苯并[d][1,3]二氧杂环戊烯-5-羧酸甲酯 、 联硼酸新戊二醇酯 在 1,1'-双(二苯膦基)二茂铁二氯化钯(II)二氯甲烷复合物 、 potassium acetate 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以88%的产率得到methyl 6-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzo[d][1,3]dioxole-5-carboxylate
  参考文献：
  名称：

  Rapid and Enantioselective Assembly of the Lycorine Framework Using Chemoenzymatic Techniques

  摘要：

  The pentacyclic framework associated with the alkaloid (-)-lycorine (1) can be assembled in as few as six steps from the enantiomerically pure cis-1,2-dihydrocatechol 3 which is itself readily available on a large scale through the whole-cell biotransformation of bromobenzene. The methodology has been used in developing the first synthesis of compound 2, a derivative of lycorine.

  DOI：

  10.1021/ol901364n

文献信息

• Synthesis of the Enantiomer of the Structure Assigned to the Natural Product Nobilisitine A
  作者：Brett D. Schwartz、Matthew T. Jones、Martin G. Banwell、Ian A. Cade

  DOI：10.1021/ol102249q

  日期：2010.11.19

  of the enantiomer of the structure, 1, assigned to the natural product nobilisitine A has been accomplished using the enantiomerically pure cis-1,2-dihydrocatechol 4 as starting material. The 1H and 13C NMR spectral data derived from compound ent-1 do not match those reported for the natural product, thus suggesting its structure has been incorrectly assigned.

  使用对映体纯的顺式1,2,2-二氢邻苯二酚4作为起始原料，完成了分配给天然产物胭脂碱A的结构1的对映体的合成。从化合物ent-1衍生的1H和13C NMR光谱数据与天然产物报道的数据不匹配，因此表明其结构已被错误分配。
• Biomimetic Total Synthesis of the Pentacyclic <i>Amaryllidaceae</i> Alkaloid Derivative Gracilamine
  作者：Nadia (Yuqian) Gao、Martin G. Banwell、Anthony C. Willis

  DOI：10.1021/acs.orglett.6b03465

  日期：2017.1.6

  with ethyl l-leucinate, engages in a stereoselective intramolecular cycloaddition reaction to give adduct 23 that has been elaborated, over eight steps, into the racemic modification of the alkaloid derivative gracilamine (1). The formation of this ylide and its conversion into isomer 23 mimics the proposed biogenesis of the pentacyclic framework of compound 1.

  通过相应的含醛的C 3a-芳基六氢吲哚与1-亮氨酸乙酯的席夫碱缩合反应制得的所示的甲亚胺叶立德参与立体选择性的分子内环加成反应，得到加成物23，该加成物在8个步骤中被精制为外消旋体生物碱衍生物gracilamine（1）。该叶立德的形成及其向异构体23的转化模拟了化合物1的五环骨架的拟生物发生。
• The Pd-Catalyzed Alder - Ene Reactions of N-Protected and Propargylated 1-Amino-2-aryl-2-cyclohexenes as a New Route to C3a-Arylhexahydroindoles: Towards the Total Synthesis of Tazettine
  作者：Anna L. Lehmann、Anthony C. Willis、Martin G. Banwell

  DOI：10.1071/ch10359

  日期：——

  A series of N-protected and propargylated 1-amino-2-aryl-2-cyclohexenes (4) has been prepared. Several of these have been shown to undergo an intramolecular Alder–ene reaction in the presence of palladium acetate and the ligand BBEDA to afford C3a-arylhexahydroindoles of the general form 1. Certain of these products may serve as precursors to the alkaloid tazettine (2).

  已经制备了一系列的N-保护的和炔丙基化的1-氨基-2-芳基-2-环己烯（4）。已显示其中一些在乙酸钯和配体BBEDA的存在下进行分子内Alder-ene反应，从而得到通式1的C3a-芳基六氢吲哚。这些产品中的某些可以用作生物碱他扎汀的前体（2）。
• A Total Synthesis of (±)-3-<i>O</i>-Demethylmacronine through Rearrangement of a Precursor Embodying the Haemanthidine Alkaloid Framework
  作者：Xiang Ma、Nadia Gao、Martin G. Banwell、Paul D. Carr、Anthony C. Willis

  DOI：10.1021/acs.joc.7b00340

  日期：2017.4.21

  A total synthesis of the racemic modification, (±)-2, of the tazettine-type alkaloid 3-O-demethylmacronine is described. The key steps are an intramolecular Alder-ene (IMAE) reaction and a lactam-to-lactone rearrangement of tetracycle 13, a compound that embodies the haemanthidine alkaloid framework.

  描述了他扎汀型生物碱3- O-脱甲基MAcronine的外消旋修饰物（±）-2的全合成。关键步骤是分子内Alder-ene（IMAE）反应和四环素13的内酰胺至内酯重排，该四环素体现了曼地替啶生物碱骨架。
• A Chemoenzymatic Total Synthesis of (+)-Clividine
  作者：Lorenzo V. White、Brett D. Schwartz、Martin G. Banwell、Anthony C. Willis

  DOI：10.1021/jo201005d

  日期：2011.8.5

  The title compound, ent-1, the non-natural enantiomeric form of the lycorenine-type alkaloid (-)-clividine (1), has been prepared using the enantiomerically pure (ee >99.8%) cis-1,2-dihydrocatechol 3 as starting material. A key feature associated with the closing stages of the synthesis involved the diastereoselective addition of a nitrogen-centered radical onto a pendant cyclohexene to establish the cis-fused D-ring and the required stereochemistry at C11b in the final product ent-1.