Tributyl-{2-[(R)-3-((2R,3R,4R)-4-dimethylamino-5-methoxy-2,3-bis-triethylsilanyloxy-pentanoylamino)-1-methyl-propyl]-oxazol-4-ylmethyl}-phosphonium; bromide | 139461-87-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: Tributyl-{2-[(R)-3-((2R,3R,4R)-4-dimethylamino-5-methoxy-2,3-bis-triethylsilanyloxy-pentanoylamino)-1-methyl-propyl]-oxazol-4-ylmethyl}-phosphonium; bromide
• CAS: 139461-87-3
• 化学式: Br*C₄₀H₈₃N₃O₅PSi₂
• 分子量: 853.165
• InChiKey: SGJSXNMBQDKMCD-VBRKIIPYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.56
• 重原子数：
  52.0
• 可旋转键数：
  31.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  86.06
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  Tributyl-{2-[(R)-3-((2R,3R,4R)-4-dimethylamino-5-methoxy-2,3-bis-triethylsilanyloxy-pentanoylamino)-1-methyl-propyl]-oxazol-4-ylmethyl}-phosphonium; bromide 、 <2Z,4E,6E,8E,10S,11S,12R,13R,15R,15(2S,3S,5S,7R,8R,9S)>-15-<9-(tert-butyldimethylsiloxy)-7-(2-oxoethyl)-3--4,4,8-trimethyl-1,6-dioxaspiro<4.5>dec-2-yl>-11,13-bis(tert-butyldimethylsiloxy)-15-methoxy-3,7,8,10,12-pentamethy 在 lithium diisopropyl amide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 以65%的产率得到
  参考文献：
  名称：

  Total synthesis of (+)-calyculin A

  摘要：

  A convergent asymmetric synthesis of the marine natural product calyculin A has been accomplished through the union of the two subunits comprising the C1-C25 and C26-C37 portions of the molecule. These fragments were constructed utilizing auxiliary-based asymmetric aldol, alkylation, hydroxylation, and Michael reactions to establish 10 of the 15 stereogenic centers, The remaining chirality was incorporated through internal asymmetric induction. Stereoselective Wittig coupling of the two fragments and subsequent deprotection provided synthetic calyculin A. The spectral properties of the synthetic material were in complete agreement with those of the natural material except for the optical rotation which was equal and opposite in sign to that of the natural material. The absolute configuration of (-)-calyculin A has thus been shown to be opposite to that illustrated in structure 1.

  DOI：

  10.1021/ja00050a024
• 作为产物：
  描述：

  <2S,2(2R)>-methyl 2-<(4-((tert-butoxycarbonyl)amino)-2-methyl-1-oxobutyl)amino>-3-hydroxypropanoate 在 palladium on activated charcoal 吡啶 、 2,6-二甲基吡啶 、 盐酸 、 4-二甲氨基吡啶 、 氯化亚砜 、 氢气 、 双氧水 、 三甲基铝 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 水 、 溶剂黄146 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 39.0h， 生成 Tributyl-{2-[(R)-3-((2R,3R,4R)-4-dimethylamino-5-methoxy-2,3-bis-triethylsilanyloxy-pentanoylamino)-1-methyl-propyl]-oxazol-4-ylmethyl}-phosphonium; bromide
  参考文献：
  名称：

  Asymmetric synthesis of calyculin A. 2. The C26-C37 .gamma.-amino acid fragments

  摘要：

  New chiral imide enolate alkylation, aldol, and Michael addition bond constructions have been employed in the asymmetric synthesis of the C26-C37 portion of calyculin A.

  DOI：

  10.1021/jo00033a010

文献信息

• Asymmetric synthesis of calyculin A. 3. Assemblage of the calyculin skeleton and the introduction of a new phosphate monoester synthesis
  作者：David A. Evans、James R. Gage、James L. Leighton

  DOI：10.1021/jo00033a011

  日期：1992.3

  The synthesis of a fully protected analogue of calyculin A has been accomplished using a Wittig reaction to couple two fragments comprising the C1-C25 and C26-C37 portions of calyculin A. Associated model studies on the incorporation of the C17 phosphate monoester moiety are also described.