tert-butyl-[(2R,3R,4R,6R)-3-[tert-butyl(dimethyl)silyl]oxy-2-methyl-6-(1,5,9,10-tetramethoxyanthracen-2-yl)oxan-4-yl]oxy-dimethylsilane | 136459-94-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: tert-butyl-[(2R,3R,4R,6R)-3-[tert-butyl(dimethyl)silyl]oxy-2-methyl-6-(1,5,9,10-tetramethoxyanthracen-2-yl)oxan-4-yl]oxy-dimethylsilane
• CAS: 136459-94-4
• 化学式: C₃₆H₅₆O₇Si₂
• 分子量: 657.007
• InChiKey: PRYNNWILVJXPCF-PVXRPORASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.66
• 重原子数：
  45
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  64.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  tert-butyl-[(2R,3R,4R,6R)-3-[tert-butyl(dimethyl)silyl]oxy-2-methyl-6-(1,5,9,10-tetramethoxyanthracen-2-yl)oxan-4-yl]oxy-dimethylsilane 在 吡啶 、 4-二甲氨基吡啶 、 ammonium cerium(IV) nitrate 作用下， 以 水 、 乙腈 为溶剂， 反应 0.25h， 生成 Benzoic acid (R)-2-benzyloxy-1-{6-[(2R,4R,5R,6R)-4,5-bis-(tert-butyl-dimethyl-silanyloxy)-6-methyl-tetrahydro-pyran-2-yl]-1,5-dimethoxy-9,10-dioxo-9,10-dihydro-anthracen-2-yl}-2-methyl-pent-4-enyl ester
  参考文献：
  名称：

  Convergent total synthesis of vineomycinone B2 methyl ester and its C(12)-epimer

  摘要：

  Total syntheses of vineomycinone B2 methyl ester (7) and its C(12)-epimer (epi-7) have been completed. The key reaction for construction of the aryl C-glycoside linkage is the O --> C-glycoside rearrangement starting from D-olivosyl fluoride derivative 11 and anthrol derivative 21, which provides the regio- and stereocontrolled formation of the aryl C-glycoside sector of the target. The combination of Cp2HfCl2-AgClO4 serves as a particularly efficient promoter for this reaction. An extensive model study for attaching the side chain is presented. The Lochmann-Schlosser base cleanly effects ortho metalation of anthracene derivatives 19 and 20. The metalated species can be trapped as stannyl derivatives, from which the corresponding aryllithium species are generated by using n-BuLi or preferably MeLi in toluene. These specific reaction conditions are necessary to suppress the abnormal reaction of RLi reagents at the C(9)/C(10)-positions of the anthracenes. Coupling of the side chain moiety was efficiently carried out by such metalation of anthracene derivative 25 followed by reaction with chiral aldehyde (S)-29. The chiral aldehyde was derived from enantiomerically pure acid (S)-37 obtained by enzymatic kinetic resolution. Deoxygenation of the benzylic alcohol function followed by several steps allowed the total ynthesis of 7. Starting from (R)-aldehyde 29, the same sequence of reactions accomplished the total synthesis of epi-7. The epi series of intermediates provided firm evidence for the stereochemical homogeneity of synthetic 7.

  DOI：

  10.1021/ja00018a041
• 作为产物：
  描述：

  1-(methoxymethoxy)-5,9,10-trimethoxyanthracene 在 2,6-二甲基吡啶 、 sodium hydroxide 、 二氯二茂铪 、 4 A molecular sieve 、 三氟化硼乙醚 、 silver perchlorate 、 sodium hydride 、 乙硫醇 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 7.66h， 生成 tert-butyl-[(2R,3R,4R,6R)-3-[tert-butyl(dimethyl)silyl]oxy-2-methyl-6-(1,5,9,10-tetramethoxyanthracen-2-yl)oxan-4-yl]oxy-dimethylsilane
  参考文献：
  名称：

  Convergent total synthesis of vineomycinone B2 methyl ester and its C(12)-epimer

  摘要：

  Total syntheses of vineomycinone B2 methyl ester (7) and its C(12)-epimer (epi-7) have been completed. The key reaction for construction of the aryl C-glycoside linkage is the O --> C-glycoside rearrangement starting from D-olivosyl fluoride derivative 11 and anthrol derivative 21, which provides the regio- and stereocontrolled formation of the aryl C-glycoside sector of the target. The combination of Cp2HfCl2-AgClO4 serves as a particularly efficient promoter for this reaction. An extensive model study for attaching the side chain is presented. The Lochmann-Schlosser base cleanly effects ortho metalation of anthracene derivatives 19 and 20. The metalated species can be trapped as stannyl derivatives, from which the corresponding aryllithium species are generated by using n-BuLi or preferably MeLi in toluene. These specific reaction conditions are necessary to suppress the abnormal reaction of RLi reagents at the C(9)/C(10)-positions of the anthracenes. Coupling of the side chain moiety was efficiently carried out by such metalation of anthracene derivative 25 followed by reaction with chiral aldehyde (S)-29. The chiral aldehyde was derived from enantiomerically pure acid (S)-37 obtained by enzymatic kinetic resolution. Deoxygenation of the benzylic alcohol function followed by several steps allowed the total ynthesis of 7. Starting from (R)-aldehyde 29, the same sequence of reactions accomplished the total synthesis of epi-7. The epi series of intermediates provided firm evidence for the stereochemical homogeneity of synthetic 7.

  DOI：

  10.1021/ja00018a041

文献信息

• Total Synthesis of Vineomycin B₂
  作者：Shunichi Kusumi、Satoshi Tomono、Shunsuke Okuzawa、Erika Kaneko、Takashi Ueda、Kaname Sasaki、Daisuke Takahashi、Kazunobu Toshima

  DOI：10.1021/ja407827n

  日期：2013.10.23

  The first total synthesis of vineomycin B2 (1) has been accomplished. The aglycon segment, a vineomycinone B2 derivative, and the glycon segment, an α-L-acurosyl-L-rhodinose derivative, were prepared via C-glycosylation using an unprotected sugar and powerful chemoselective O-glycosylation using a 2,3-unsaturated sugar, respectively, as the key steps. Furthermore, effective and simultaneous introduction

  葡萄霉素B2（1）的首次全合成已经完成。苷元片段（葡萄霉素 B2 衍生物）和糖苷元片段（α-L-acurosyl-L-蔷薇糖衍生物）是通过使用未保护糖的 C-糖基化和使用 2,3-不饱和糖的强大化学选择性 O-糖基化制备的，分别作为关键步骤。此外，通过浓度控制的糖基化有效且同时将两个糖基部分引入苷元部分导致了 1 的全合成。