2,4,6-tris(benzyloxy)benzaldehyde | 135351-89-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2,4,6-tris(benzyloxy)benzaldehyde
• 英文别名: 2,4,6-tris(O-benzyl)benzaldehyde；2,4,6-Tribenzyloxybenzaldehyde；2,4,6-tris(phenylmethoxy)benzaldehyde
• CAS: 135351-89-2
• 化学式: C₂₈H₂₄O₄
• 分子量: 424.496
• InChiKey: ROMAJIADALKFCR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  32
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,4,6-tris(benzyloxy)benzaldehyde 在 manganese(IV) oxide 、 potassium phosphate 、 正丁基锂 、 palladium diacetate 、 三苯基膦 、 silver carbonate 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 17.5h， 生成 (2-(4-methoxyphenyl)-5-methylbenzofuran-3-yl)(2,4,6-tris(benzyloxy)phenyl)methanone
  参考文献：
  名称：

  通过分子内Heck偶联的2-取代3-功能化的苯并呋喃的构建：瑞香酚B对映体选择性合成的应用。

  摘要：

  利用分子内的Heck反应，开发了一种用于合成2-取代的3-官能化的苯并呋喃的新方法，该方法还被用于Daphnodorin B的首次对映选择性全合成。

  DOI：

  10.1021/ol4021095
• 作为产物：
  描述：

  间苯三酚 在 potassium carbonate 、 三氯氧磷 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 51.0h， 生成 2,4,6-tris(benzyloxy)benzaldehyde
  参考文献：
  名称：

  通过分子内Heck偶联的2-取代3-功能化的苯并呋喃的构建：瑞香酚B对映体选择性合成的应用。

  摘要：

  利用分子内的Heck反应，开发了一种用于合成2-取代的3-官能化的苯并呋喃的新方法，该方法还被用于Daphnodorin B的首次对映选择性全合成。

  DOI：

  10.1021/ol4021095

文献信息

• Synthesis of facially-encumbered porphyrins. An approach to light-harvesting antenna complexes
  作者：Richard W. Wagner、James Ruffing、Bradly V. Breakwell、Jonathan S. Lindsey

  DOI：10.1016/s0040-4039(00)74308-5

  日期：1991.4

  2,6-di- and 2,4,6-tri-benzyloxybenzaldehydes are converted to the respective octa- and dodeca-benzyloxy porphyrins in 9–52% yields via the two-step one-flask room-temperature porphyrin synthesis.

  通过两步式一瓶室温卟啉合成，将2，6-二和2,4,6-三苄氧基苯甲醛以9-52％的产率转化为相应的八-和十二-苄氧基卟啉。
• Total synthesis of Daphnodorin A
  作者：Hu Yuan、Kaijian Bi、Wanlin Chang、Rongcai Yue、Bo Li、Ji Ye、Qingyan Sun、Huizi Jin、Lei Shan、Weidong Zhang

  DOI：10.1016/j.tet.2014.10.010

  日期：2014.11

  A total synthesis of Daphnodorin A, a member of the Daphnodorins, was accomplished. Key features of the synthetic strategy include construction of 2-substituted-3-functionalized benzofuran via intramolecular Heck reaction and a mild Barton–McCombie deoxygenation process mediated by triethylborane. The total synthesis provided Daphnodorin A in 19.7% or 5.6% overall yield over 7 or 15 steps.

  Daphnodorin A的一个成员，Daphnodorin A的全合成完成了。合成策略的关键特征包括通过分子内Heck反应和由三乙基硼烷介导的温和的Barton-McCombie脱氧过程来构建2取代3官能化的苯并呋喃。总的合成在7或15个步骤中提供了达芙蓉素A的总产率为19.7％或5.6％。
• Ordering the Reductive and Cytochrome P450 Oxidative Steps in Demethylsterigmatocystin Formation Yields General Insights into the Biosynthesis of Aflatoxin and Related Fungal Metabolites
  作者：Kevin M. Henry、Craig A. Townsend

  DOI：10.1021/ja0455188

  日期：2005.3.1

  beyond the first polyketide intermediate. Central among these is the rearrangement of the anthraqinone versicolorin A to the xanthone demethylsterigmatocystin. Genetic evidence strongly suggests that two enzymes are required for this process, a cytochrome P450, AflN, and a probable NADPH-dependent oxidoreductase, AflM. Given the overall redox change evident in this skeletal rearrangement, two rounds of

  强环境致癌物黄曲霉毒素 B1 的生物合成涉及约。超出第一个聚酮化合物中间体 15 个步骤。其中的核心是蒽醌杂色素 A 重排为氧杂蒽酮去甲基杂色藻素。遗传证据强烈表明该过程需要两种酶，细胞色素 P450 AflN 和可能依赖 NADPH 的氧化还原酶 AflM。鉴于此骨架重排中明显的整体氧化还原变化，必然会发生两轮氧化和还原。早期的实验表明，杂色素 A 的还原脱氧不是第一步。在本报告中，我们考虑了一种机制替代方案，即 AflM 介导的还原是在形成呫吨酮中间体之前这三个反应中的最后一个。为此，9-羟基二氢去甲基sterigmatocystin 及其9-脱氧类似物（一种已建立的黄曲霉毒素前体）是通过全合成制备的。在“角形”合成氧杂蒽酮靶的最终分离过程中，发现酸催化促进它们的异构化为热力学有利的“线性”氧杂蒽酮。9-羟基-和9-脱氧氧杂蒽酮的全细胞和地面细胞孵育是用在该途径的第一步阻断的寄生曲霉突
• Synthesis of porphyrins tailored with eight facially-encumbering groups. An approach to solid-state light-harvesting complexes
  作者：Richard W. Wagner、Jonathan S. Lindsey、Ilona Turowska-Tyrk、W.Robert Scheidt

  DOI：10.1016/s0040-4020(01)89413-8

  日期：——

  Synthetic models of the photosynthetic antenna complexes must achieve long-range 3-dimensional order encompassing a large number of porphyrinic pigments with limited direct contact of the pigments. In order to develop solid-state antenna complexes, we have synthesized porphyrins bearing benzyloxy groups projecting over both faces and optionally also around the periphery of the porphyrin. Routes have been established for prefunctionalizing benzaldehydes with various benzyloxy groups. Reaction of 2,6-bis, 3,5-bis, or 2,4,6-tris(benzyloxy)benzaldehydes with pyrrole via the room temperature two-step one-flask porphyrin reaction provides direct access to the facially-encumbered porphyrins. The benzyloxybenzaldehydes react as efficiently as methoxybenzaldehydes, indicating the utility of the -OCH2- unit for introducing large substituents near the face of the porphyrin. The octakis and dodecakis(benzyloxy)porphyrins exhibit characteristic porphyrin absorption and fluorescence properties in solution. The crystal structure of meso-tetrakis[2,6-bis(2,3 4,5,6-pentafluorobenzyloxy)phenyl] porphyrin has been determined. The pentafluorobenzyloxy substituents provide a cavity on each side of the porphyrin plane which has an approximate cylindrical shape with a diameter of similar to 7.5 Angstrom and a height of greater than or equal to 4.5 Angstrom. The porphyrin core parameters are those obtained for free base derivatives in which the inner hydrogen atoms are ordered. Crystal data: a = 14.759(1) Angstrom, b = 25.519 (2) Angstrom, c = 13.100(1) Angstrom, alpha = 100.04(1), beta = 99.83 (1), gamma = 88.25(1), V = 4767.3 (6) Angstrom(3), all measurements at 127 K, triclinic, space group P-1(-), Z = 2 R(1)(F) = 0.097, for 10020 ''observed'' data, and wR(2)(F-2) = 0.275 for 17761 total unique (all) data.
• Construction of 2-Substituted-3-Functionalized Benzofurans via Intramolecular Heck Coupling: Application to Enantioselective Total Synthesis of Daphnodorin B
  作者：Hu Yuan、Kai-Jian Bi、Bo Li、Rong-Cai Yue、Ji Ye、Yun-Heng Shen、Lei Shan、Hui-Zi Jin、Qing-Yan Sun、Wei-Dong Zhang

  DOI：10.1021/ol4021095

  日期：2013.9.20

  A novel approach was developed for the synthesis of 2-substituted-3-functionalized benzofurans, using an intramolecular Heck reaction which was further applied in the first enantioselective total synthesis of Daphnodorin B.

  利用分子内的Heck反应，开发了一种用于合成2-取代的3-官能化的苯并呋喃的新方法，该方法还被用于Daphnodorin B的首次对映选择性全合成。