methyl (3R)-4-[6-[(2R,4R,5R,6R)-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]-6-methyloxan-2-yl]-1,5-dimethoxy-9,10-dioxoanthracen-2-yl]-3-hydroxy-3-methylbutanoate | 136460-03-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 角环素
• 英文名称: methyl (3R)-4-[6-[(2R,4R,5R,6R)-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]-6-methyloxan-2-yl]-1,5-dimethoxy-9,10-dioxoanthracen-2-yl]-3-hydroxy-3-methylbutanoate
• CAS: 136460-03-2
• 化学式: C₄₀H₆₀O₁₀Si₂
• 分子量: 757.081
• InChiKey: AIRBDLKUHCSDLM-PRTGKWDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.97
• 重原子数：
  52.0
• 可旋转键数：
  11.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  126.82
• 氢给体数：
  1.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  methyl (3R)-4-[6-[(2R,4R,5R,6R)-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]-6-methyloxan-2-yl]-1,5-dimethoxy-9,10-dioxoanthracen-2-yl]-3-hydroxy-3-methylbutanoate 在 三溴化硼 作用下， 以 二氯甲烷 为溶剂， 反应 0.42h， 以90%的产率得到vineomycinone B2 methyl 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 吡啶 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 sodium hydroxide 、 sodium dithionite 、 phosphate buffer 、 二氯二茂铪 、 ammonium cerium(IV) nitrate 、 4 A molecular sieve 、 三氟化硼乙醚 、 氧气 、 silver perchlorate 、 乙酸酐 、 sodium hydride 、 臭氧 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 乙硫醇 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 16.33h， 生成 methyl (3R)-4-[6-[(2R,4R,5R,6R)-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]-6-methyloxan-2-yl]-1,5-dimethoxy-9,10-dioxoanthracen-2-yl]-3-hydroxy-3-methylbutanoate
  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