N-<(12aS,4R,12R,11bR,3aR,4aR)-4-(methoxymethoxy)-2,2-dimethyl-6-oxo(4,12,11b,12a,3a,4a-hexahydro-9H-1,3-dioxoleno<4",5"-7',6'>isochromano<4',3'-5,4>benzo<1,2-d>-1,3-dioxolan-12-yl)>-2,2,2-trifluoroacetamide | 236388-01-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: N-<(12aS,4R,12R,11bR,3aR,4aR)-4-(methoxymethoxy)-2,2-dimethyl-6-oxo(4,12,11b,12a,3a,4a-hexahydro-9H-1,3-dioxoleno<4",5"-7',6'>isochromano<4',3'-5,4>benzo<1,2-d>-1,3-dioxolan-12-yl)>-2,2,2-trifluoroacetamide
• 英文别名: 2,2,2-trifluoro-N-[(2R,3R,4S,8S,9S,10R)-9-(methoxymethoxy)-6,6-dimethyl-12-oxo-5,7,11,16,18-pentaoxapentacyclo[11.7.0.02,10.04,8.015,19]icosa-1(20),13,15(19)-trien-3-yl]acetamide
• CAS: 236388-01-5
• 化学式: C₂₁H₂₂F₃NO₉
• 分子量: 489.402
• InChiKey: QZMCITZETJXWCU-FFRIZKCHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  34
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  111
• 氢给体数：
  1
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  N-<(12aS,4R,12R,11bR,3aR,4aR)-4-(methoxymethoxy)-2,2-dimethyl-6-oxo(4,12,11b,12a,3a,4a-hexahydro-9H-1,3-dioxoleno<4",5"-7',6'>isochromano<4',3'-5,4>benzo<1,2-d>-1,3-dioxolan-12-yl)>-2,2,2-trifluoroacetamide 在 吡啶 、 4-二甲氨基吡啶 、 DOWEX-H⁺ (50W-X₈) 、 potassium carbonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 31.5h， 生成 (1R,2S,3S,4S,4aR,11bR)-1,2,3,4-Tetraacetoxy-1,3,4,4a,5,11b-hexahydro<1,3>dioxolo<4,5-j>phenanthridin-6(2H)-on
  参考文献：
  名称：

  Diastereoselective 6-exo Radical Cyclizations of Oxime Ethers:  Total Synthesis of 7-Deoxypancratistatin

  摘要：

  The development of an approach leading to the total synthesis of 7-deoxypancratistatin is described. The key features of the approach include a 6-exo radical cyclization reaction between a benzylic radical and an O-benzyloxime ether to establish the C-4a-C-10b bond. The stereochemistry of this reaction was examined in both acyclic radical precursors and ones in which the aryl moiety was tethered to the C-1 oxygen substituent. It was found that the use of such a tether was essential to obtain the stereochemical result required for the synthesis. The correct absolute and relative configurations at the hydroxylated carbons C-1-C-4 were obtained using D-gulonolactone as the source of C-10b-C-4a.

  DOI：

  10.1021/jo9902042
• 作为产物：
  描述：

  2,3-Isopropylidene-D-gulono-γ-lactone 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 sodium chlorite 、 sodium tetrahydroborate 、 potassium dihydrogenphosphate 、 正丁基锂 、 N-甲基吲哚酮 、 samarium diiodide 、 四丙基高钌酸铵 、 偶氮二异丁腈 、 氢氟酸 、 四丁基氟化铵 、 三正丁基氢锡 、 二异丁基氢化铝 、 N,N-二异丙基乙胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 1,2-二氯乙烷 、 甲苯 为溶剂， 生成 N-<(12aS,4R,12R,11bR,3aR,4aR)-4-(methoxymethoxy)-2,2-dimethyl-6-oxo(4,12,11b,12a,3a,4a-hexahydro-9H-1,3-dioxoleno<4",5"-7',6'>isochromano<4',3'-5,4>benzo<1,2-d>-1,3-dioxolan-12-yl)>-2,2,2-trifluoroacetamide
  参考文献：
  名称：

  Total Synthesis of (+)-7-Deoxypancratistatin: A Radical Cyclization Approach

  摘要：

  DOI：

  10.1021/ja00132a047

文献信息

• Reductive cleavage of NO bonds in hydroxylamine and hydroxamic acid derivatives using SmI2/THF
  作者：Gary E. Keck、Stanton F. McHardy、Travis T. Wager

  DOI：10.1016/0040-4039(95)01557-4

  日期：1995.10

  The title reaction affords a general method for the reductive cleavage of NO bonds, and is successful in some cases where established methods fail.

  标题反应提供了还原NO键的一般方法，并且在某些已建立方法失败的情况下是成功的。
• Diastereoselective 6-<i>e</i><i>xo</i> Radical Cyclizations of Oxime Ethers:  Total Synthesis of 7-Deoxypancratistatin
  作者：Gary E. Keck、Stanton F. McHardy、Jerry A. Murry

  DOI：10.1021/jo9902042

  日期：1999.6.1

  The development of an approach leading to the total synthesis of 7-deoxypancratistatin is described. The key features of the approach include a 6-exo radical cyclization reaction between a benzylic radical and an O-benzyloxime ether to establish the C-4a-C-10b bond. The stereochemistry of this reaction was examined in both acyclic radical precursors and ones in which the aryl moiety was tethered to the C-1 oxygen substituent. It was found that the use of such a tether was essential to obtain the stereochemical result required for the synthesis. The correct absolute and relative configurations at the hydroxylated carbons C-1-C-4 were obtained using D-gulonolactone as the source of C-10b-C-4a.
• Total Synthesis of (+)-7-Deoxypancratistatin: A Radical Cyclization Approach
  作者：Gary E. Keck、Stanton F. McHardy、Jerry A. Murry

  DOI：10.1021/ja00132a047

  日期：1995.7