per-O-methyltellimagrandid I

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 单宁
• 英文名称: per-O-methyltellimagrandid I
• 英文别名: [(10R,11S,12R,13S,15R)-3,4,5,13,21,22,23-heptamethoxy-8,18-dioxo-12-(3,4,5-trimethoxybenzoyl)oxy-9,14,17-trioxatetracyclo[17.4.0.02,7.010,15]tricosa-1(23),2,4,6,19,21-hexaen-11-yl] 3,4,5-trimethoxybenzoate
• 化学式: C₄₇H₅₂O₂₂
• 分子量: 968.917
• InChiKey: JYJCWEWJRGFVSS-WFNFSCCGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  69
• 可旋转键数：
  19
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  234
• 氢给体数：
  0
• 氢受体数：
  22

反应信息

• 作为产物：
  描述：

  alpha-甲基葡萄糖甙 在 4-二甲氨基吡啶 、 vanadium oxyfluoride 、 4-(dimethylamino)pyridine hydrochloride 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 per-O-methyltellimagrandid I
  参考文献：
  名称：

  鞣花单宁化学。鞣花单宁天然产物 Tellimagrandin I 的首次全化学合成

  摘要：

  Tellimagrandin I 是通过两种不同的生物遗传学模式合成的。一种路线的特色是在葡萄糖衍生底物中的 O(4) 和 O(6) 没食子酰部分之间的非对映选择性没食子酰酯耦合，在 0(2) 和 0(3) 上具有额外的受保护没食子酰基团。第二种途径依赖于完全非对映选择性和区域选择性的基于 Pb(OAc) 4 的氧化偶联，仅在葡萄糖衍生底物中的 O(4) 和 O(6) 没食子酰酯之间进行氧化偶联，该底物具有 O(2)- O(6)。基于分子力学的构象分析为观察到的选择性提供了依据

  DOI：

  10.1021/ja00084a015

文献信息

• Tannins and Related Polyphenols of Lythraceous Plants. Part2. Woodfordin D and Oenothein A, Trimeric Hydrolyzable Tannins of Macro-Ring Structure with Antitumor Activity.
  作者：Takashi YOSHIDA、Tong CHOU、Muneto MATSUDA、Taeko YASUHARA、Kazufumi YAZAKI、Tsutomu HATANO、Aya NITTA、Takuo OKUDA

  DOI：10.1248/cpb.39.1157

  日期：——

  trimeric hydrolyzable tannins, woodfordin D (5) and oenothein A (13), were isolated from the dried flowers of Woodfordia fruticosa, and their macrocyclic structures, which have a novel constituent unit (woodfordinoyl group) connecting the monomers, have been elucidated on the basis of spectral and chemical evidence. Oenothein A (13) was also isolated from the leaves of Oenothera biennis.

  从桔梗的干燥花中分离出两种新的抗肿瘤三聚体可水解单宁，伍德福德D（5）和卵磷脂A（13），它们的大环结构具有连接单体的新组成单元（伍德福德基）。根据光谱和化学证据进行了阐明。还从月见草的叶子中分离出Oenothein A（13）。
• Structure of gemin A, a new dimeric ellagitannin having α- and β-glucose cores
  作者：Takashi Yoshida、Takuo Okuda、M. Usman Memon、Tetsuro Shingu

  DOI：10.1039/c39820000351

  日期：——

  A dimeric ellagitannin gemin A (1), has been isolated from Geum japonicum Thunb., and its structure, which contains α- and β-glucose cores, has been elucidated.

  二聚体鞣花单宁双核蛋白A（1）已从日本锦葵中分离出来，其结构已阐明，该结构包含α-和β-葡萄糖核心。
• Studies Relevant to Ellagitannin Chemistry:  Highly Diastereoselective Intramolecular Biaryl Coupling in Bis(iodotrimethoxybenzoyl) Hexopyranose Derivatives
  作者：Dongcheng Dai、Olivier R. Martin

  DOI：10.1021/jo971722k

  日期：1998.10.1

  Internal biaryl coupling reactions of carbohydrate derivatives carrying two 2-iodo-3,4,5-trimethoxybenzoyl groups under Ullmann conditions were investigated. With substituents at positions 2,3 or 4,6 of a D-glucopyranoside, 2,3 of a D-mannopyranoside, and 3,4 of a D-galactopyranoside, the coupling was found to proceed with a very high degree of stereoselectivity, leading exclusively to the (S)-epimer of the resulting hexamethoxydiphenoyl residue from the D-gluco and D-galacto substrates, and to the (R)-epimer from the D-manno substrate. With substituents at positions 2,4 of D-glucopyranose derivatives in the C-1(4) conformation and at positions 5,6 of a D-glucofuranose derivative, the coupling proceeded efficiently but with modest stereoselectivity. Some deiodinated starting material was formed as a byproduct in all reactions. These results are relevant to ellagitannin chemistry in that they provide further understanding of the structural requirements for highly diastereoselective biaryl coupling within carbohydrate units. In addition, the efficient, complementary reactions of the D-manno and D-galacto substrates provide a method for the enantioselective synthesis of hexamethoxydiphenoic acid derivatives.
• A Rapid Total Synthesis of an Ellagitannin
  作者：Todd D. Nelson、A. I. Meyers

  DOI：10.1021/jo00088a046

  日期：1994.5

  The ellagitannins are galloyl esters of glucose that contain at least one chiral biaryl (digalloyl) subunit. Included in this family are the tellimagrandins (1-3). The first asymmetric synthesis of (S)-4,4',5,5',6,6'-hexamethoxy-2,2'-diphenic acid, a ubiquitous subunit in ellagitannins, is reported by utilization of an intermolecular oxazoline-mediated asymmetric Ullmann coupling. Attachment of this acid to an appropriate glucose core resulted in the synthesis of an ellagitannin.
• Ellagitannin Chemistry. The First Total Chemical Synthesis of an Ellagitannin Natural Product, Tellimagrandin I
  作者：Ken S. Feldman、Susan M. Ensel、Robert D. Minard

  DOI：10.1021/ja00084a015

  日期：1994.3

  Tellimagrandin I was synthesized by two different biogenetically patterned routes. One route featured diastereoselective galloyl ester coupling between the O(4) and O(6) galloyl moieties in a glucose-derived substrate bearing additional protected galloyl groups on 0(2) and 0(3). The second route relied on a completely diastereoslective and regioselective Pb(OAc) 4 -based oxidative coupling exclusively

  Tellimagrandin I 是通过两种不同的生物遗传学模式合成的。一种路线的特色是在葡萄糖衍生底物中的 O(4) 和 O(6) 没食子酰部分之间的非对映选择性没食子酰酯耦合，在 0(2) 和 0(3) 上具有额外的受保护没食子酰基团。第二种途径依赖于完全非对映选择性和区域选择性的基于 Pb(OAc) 4 的氧化偶联，仅在葡萄糖衍生底物中的 O(4) 和 O(6) 没食子酰酯之间进行氧化偶联，该底物具有 O(2)- O(6)。基于分子力学的构象分析为观察到的选择性提供了依据