methyl 2-{(2R,3R,4R,6S)-6-[2-(benzyloxy)ethyl]-4-(triisopropylsilyl)oxy-3-methyl-2H-3,4,5,6-tetrahydropyran-2-yl}acetate | 221627-31-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 2-{(2R,3R,4R,6S)-6-[2-(benzyloxy)ethyl]-4-(triisopropylsilyl)oxy-3-methyl-2H-3,4,5,6-tetrahydropyran-2-yl}acetate
• 英文别名: methyl 2-[(2R,3R,4R,6S)-3-methyl-6-(2-phenylmethoxyethyl)-4-tri(propan-2-yl)silyloxyoxan-2-yl]acetate
• CAS: 221627-31-2
• 化学式: C₂₇H₄₆O₅Si
• 分子量: 478.745
• InChiKey: BWQMUOHTBQMGKI-BIGMCNFVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.51
• 重原子数：
  33
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2-{(2R,3R,4R,6S)-6-[2-(benzyloxy)ethyl]-4-(triisopropylsilyl)oxy-3-methyl-2H-3,4,5,6-tetrahydropyran-2-yl}acetate 在 palladium dihydroxide lithium aluminium tetrahydride 、 氢气 作用下， 以 四氢呋喃 、 乙酸乙酯 为溶剂， 反应 4.5h， 生成 2-[(2R,3R,4R,6S)-6-(2-hydroxyethyl)-4-(triisopropylsilyl)oxy-3-methyl-2H-3,4,5,6-tetrahydropyran-2-yl]ethan-1-ol
  参考文献：
  名称：

  Total Synthesis of Polycavernoside A, A Lethal Toxin of the Red Alga Polycavernosa tsudai

  摘要：

  Two approaches to the synthesis of the aglycon 120 of polycavernoside A (1) were developed, only one of which was completed. The successful "second-generation" route assembled the aglycon seco acids 102 and 106 via Nozaki-Hiyama-Kishi coupling of aldehyde 70, prepared from methyl (S)3-hydroxy-2-methylpropionate (72) and (S)-pantolactone (73), with vinyl bromide 71. The latter was obtained from a sequence which commenced from the silyl ether 24 of 3-hydroxypropionaldehyde and entailed cyclization of (Z)-zeta -hydroxy-alpha,beta-unsaturated ester 82. Regioselective Yamaguchi lactonization of trihydroxycarboxylic acids 102 and 106 and subsequent functional-group adjustments led to macrolactone 120, to which the fucopyranosylxylopyranoside moiety was attached. Stille coupling of the glycosidated aglycon 128 with dienylstannane 129 furnished polycavernoside A in a synthesis for which the longest linear sequence was 25 steps. The overall yield to lactone 120 was 4.7%.

  DOI：

  10.1021/jo0503862
• 作为产物：
  描述：

  isobutyl 5-(benzyloxy)-3-oxopentanoate 在 Ru₂Cl₄-(S)-(2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)2*NEt₃ 2,6-二甲基吡啶 、 18-冠醚-6 、 三氟甲磺酸二丁硼 、 potassium tert-butylate 、 氢气 、 三甲基铝 、 4-甲基苯磺酸吡啶 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， -78.0~55.0 ℃ 、344.74 kPa 条件下， 反应 114.0h， 生成 methyl 2-{(2R,3R,4R,6S)-6-[2-(benzyloxy)ethyl]-4-(triisopropylsilyl)oxy-3-methyl-2H-3,4,5,6-tetrahydropyran-2-yl}acetate
  参考文献：
  名称：

  Total Synthesis of Polycavernoside A, A Lethal Toxin of the Red Alga Polycavernosa tsudai

  摘要：

  Two approaches to the synthesis of the aglycon 120 of polycavernoside A (1) were developed, only one of which was completed. The successful "second-generation" route assembled the aglycon seco acids 102 and 106 via Nozaki-Hiyama-Kishi coupling of aldehyde 70, prepared from methyl (S)3-hydroxy-2-methylpropionate (72) and (S)-pantolactone (73), with vinyl bromide 71. The latter was obtained from a sequence which commenced from the silyl ether 24 of 3-hydroxypropionaldehyde and entailed cyclization of (Z)-zeta -hydroxy-alpha,beta-unsaturated ester 82. Regioselective Yamaguchi lactonization of trihydroxycarboxylic acids 102 and 106 and subsequent functional-group adjustments led to macrolactone 120, to which the fucopyranosylxylopyranoside moiety was attached. Stille coupling of the glycosidated aglycon 128 with dienylstannane 129 furnished polycavernoside A in a synthesis for which the longest linear sequence was 25 steps. The overall yield to lactone 120 was 4.7%.

  DOI：

  10.1021/jo0503862

文献信息

• Intramolecular palladium catalyzed alkoxy carbonylation of 6-hydroxy-1-octenes. Stereoselective synthesis of substituted tetrahydropyrans
  作者：James D. White、Jian Hong、Lonnie A. Robarge

  DOI：10.1016/s0040-4039(98)02693-8

  日期：1999.2

  The reaction of hydroxy alkenes 5, 7, and 8 with CO and MeOH in the presence of PdCl2 and CuCl2 gave tetrahydropyrans 9, 11, and 12, respectively. Yields were dependent upon the configuration of substituents in the hydroxy alkene; in all cases, the tetrahydropyran was produced with 2,6-cis configuration. (C) 1999 Elsevier Science Ltd. All rights reserved.