(2R)-3-[(4R,6R)-6-ethenyl-2,2,5,5-tetramethyl-1,3-dioxan-4-yl]-2-methylpropan-1-ol | 366454-98-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R)-3-[(4R,6R)-6-ethenyl-2,2,5,5-tetramethyl-1,3-dioxan-4-yl]-2-methylpropan-1-ol
• CAS: 366454-98-0
• 化学式: C₁₄H₂₆O₃
• 分子量: 242.359
• InChiKey: GKGWBRNTCLKXKF-IJLUTSLNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.74
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  38.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (2R)-3-[(4R,6R)-6-ethenyl-2,2,5,5-tetramethyl-1,3-dioxan-4-yl]-2-methylpropan-1-ol 在 2,6-二甲基吡啶 、 chromium dichloride 、 N-溴代丁二酰亚胺(NBS) 、 草酰氯 、 4 A molecular sieve 、 2,4,6-三氯苯甲酰氯 、 4-甲基苯磺酸吡啶 、 戴斯-马丁氧化剂 、 臭氧 、 二甲基亚砜 、 三乙胺 、 nickel dichloride 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 126.33h， 生成
  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：

  (2S,6R)-1-[(tert-butyldiphenylsilyl)oxy]-6-[(4-methoxybenzyl)oxy]-3-(phenylsulfonyl)-2,5,5-trimethyloct-7-en-4-one 在 samarium diiodide 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 溶剂黄146 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 tetramethylammonium triacetoxyborohydride 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 73.5h， 生成 (2R)-3-[(4R,6R)-6-ethenyl-2,2,5,5-tetramethyl-1,3-dioxan-4-yl]-2-methylpropan-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

文献信息

• Total Synthesis of the Marine Toxin Polycavernoside A via Selective Macrolactonization of a Trihydroxy Carboxylic Acid
  作者：James D. White、Paul R. Blakemore、Cindy C. Browder、Jian Hong、Christopher M. Lincoln、Pavel A. Nagornyy、Lonnie A. Robarge、Duncan J. Wardrop

  DOI：10.1021/ja011256n

  日期：2001.9.1