O-[(7R)-5-[tert-butyl(dimethyl)silyl]oxy-7-[(S)-[(4S,5S)-2,2-dimethyl-5-[(Z)-phenylmethoxyiminomethyl]-1,3-dioxolan-4-yl]-(methoxymethoxy)methyl]-7,8-dihydro-5H-[1,3]dioxolo[4,5-g]isochromen-8-yl] imidazole-1-carbothioate | 236387-99-8

• 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: O-[(7R)-5-[tert-butyl(dimethyl)silyl]oxy-7-[(S)-[(4S,5S)-2,2-dimethyl-5-[(Z)-phenylmethoxyiminomethyl]-1,3-dioxolan-4-yl]-(methoxymethoxy)methyl]-7,8-dihydro-5H-[1,3]dioxolo[4,5-g]isochromen-8-yl] imidazole-1-carbothioate
• CAS: 236387-99-8
• 化学式: C₃₆H₄₇N₃O₁₀SSi
• 分子量: 741.935
• InChiKey: CNLFLBKYHBSUGM-QSPZMVKDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.63
• 重原子数：
  51
• 可旋转键数：
  14
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  155
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  O-[(7R)-5-[tert-butyl(dimethyl)silyl]oxy-7-[(S)-[(4S,5S)-2,2-dimethyl-5-[(Z)-phenylmethoxyiminomethyl]-1,3-dioxolan-4-yl]-(methoxymethoxy)methyl]-7,8-dihydro-5H-[1,3]dioxolo[4,5-g]isochromen-8-yl] imidazole-1-carbothioate 在 吡啶 、 4-二甲氨基吡啶 、 N-甲基吲哚酮 、 samarium diiodide 、 四丙基高钌酸铵 、 偶氮二异丁腈 、 DOWEX-H⁺ (50W-X₈) 、 四丁基氟化铵 、 三正丁基氢锡 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 34.25h， 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：

  苄氧基胺盐酸盐 在 吡啶 、 4-二甲氨基吡啶 、 sodium chlorite 、 sodium tetrahydroborate 、 potassium dihydrogenphosphate 、 正丁基锂 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 氢氟酸 、 N,N-二异丙基乙胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 甲醇 、 1,2-二氯乙烷 为溶剂， 生成 O-[(7R)-5-[tert-butyl(dimethyl)silyl]oxy-7-[(S)-[(4S,5S)-2,2-dimethyl-5-[(Z)-phenylmethoxyiminomethyl]-1,3-dioxolan-4-yl]-(methoxymethoxy)methyl]-7,8-dihydro-5H-[1,3]dioxolo[4,5-g]isochromen-8-yl] imidazole-1-carbothioate
  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

• 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