1-<2-<<(tert-Butyldimethylsilyl)oxy>methyl>-4,5-(methylenedioxy)phenyl>-2-cyclohexen-1-ol | 144412-84-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 1-<2-<<(tert-Butyldimethylsilyl)oxy>methyl>-4,5-(methylenedioxy)phenyl>-2-cyclohexen-1-ol
• 英文别名: 1-[6-[[Tert-butyl(dimethyl)silyl]oxymethyl]-1,3-benzodioxol-5-yl]cyclohex-2-en-1-ol
• CAS: 144412-84-0
• 化学式: C₂₀H₃₀O₄Si
• 分子量: 362.541
• InChiKey: HIRAIOWYIAUVEP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.86
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-<2-<<(tert-Butyldimethylsilyl)oxy>methyl>-4,5-(methylenedioxy)phenyl>-2-cyclohexen-1-ol 在 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 lutidine 、 四丁基氟化铵 、 lithium perchlorate 、 叠氮化四丁基铵 、 甲基磺酰氯 、 三乙胺 、 lithium chloride 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 65.0h， 生成 (+/-)-γ-lycorane
  参考文献：
  名称：

  Synthesis of (.+-.)-.gamma.-lycorane by the intramolecular cycloaddition of an azide with an .omega.-chloroalkene

  摘要：

  Cyclization of 1-[2-(chloromethyl)-4,5-(methylenedioxy)phenyl]-3-(2-azidoethyl)cyclohex-1-ene (16) in benzene at 140-degrees-C caused the following sequence of events: (1) intramolecular 1,3-dipolar cycloaddition of the azide onto the alkene: (2) formation of an imine by loss of nitrogen from the triazoline intermediate with concomitant hydrogen migration:and (3) intramolecular N-alkylation of the imine nitrogen with the benzylic chloride. Without isolation, the resultant iminium ion was reduced with sodium borohydride to give (+/-)-gamma-lycorane (3). The cyclization precursor 16 was prepared a novel allylic substitution reaction, where the allylic alcohol 10 or the allylic acetate 11 was treated with 1-ethoxy-1-[(tert-butyldimethylsilyl)oxy]ethene and lithium perchlorate in ether to produce the gamma,delta-unsaturated ester 12. An alternative synthesis of (+/-)-gamma-lycorane (3) was accomplished using a similar 1,3-dipolar cycloaddition approach, except that the benzylic chloride functionality was absent (i.e., 26 --> 27). Reduction of the resultant imine followed by a Bischler-Napieralski cyclization gave the known lactam 31, which had previously been converted to (+/-)-gamma-lycorane.

  DOI：

  10.1021/jo00051a021
• 作为产物：
  描述：

  2-环己烯-1-酮 在 咪唑 、 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 18.08h， 生成 1-<2-<<(tert-Butyldimethylsilyl)oxy>methyl>-4,5-(methylenedioxy)phenyl>-2-cyclohexen-1-ol
  参考文献：
  名称：

  Synthesis of (.+-.)-.gamma.-lycorane by the intramolecular cycloaddition of an azide with an .omega.-chloroalkene

  摘要：

  Cyclization of 1-[2-(chloromethyl)-4,5-(methylenedioxy)phenyl]-3-(2-azidoethyl)cyclohex-1-ene (16) in benzene at 140-degrees-C caused the following sequence of events: (1) intramolecular 1,3-dipolar cycloaddition of the azide onto the alkene: (2) formation of an imine by loss of nitrogen from the triazoline intermediate with concomitant hydrogen migration:and (3) intramolecular N-alkylation of the imine nitrogen with the benzylic chloride. Without isolation, the resultant iminium ion was reduced with sodium borohydride to give (+/-)-gamma-lycorane (3). The cyclization precursor 16 was prepared a novel allylic substitution reaction, where the allylic alcohol 10 or the allylic acetate 11 was treated with 1-ethoxy-1-[(tert-butyldimethylsilyl)oxy]ethene and lithium perchlorate in ether to produce the gamma,delta-unsaturated ester 12. An alternative synthesis of (+/-)-gamma-lycorane (3) was accomplished using a similar 1,3-dipolar cycloaddition approach, except that the benzylic chloride functionality was absent (i.e., 26 --> 27). Reduction of the resultant imine followed by a Bischler-Napieralski cyclization gave the known lactam 31, which had previously been converted to (+/-)-gamma-lycorane.

  DOI：

  10.1021/jo00051a021

文献信息

• Synthesis of (.+-.)-.gamma.-lycorane by the intramolecular cycloaddition of an azide with an .omega.-chloroalkene
  作者：William H. Pearson、Jeffrey M. Schkeryantz

  DOI：10.1021/jo00051a021

  日期：1992.12

  Cyclization of 1-[2-(chloromethyl)-4,5-(methylenedioxy)phenyl]-3-(2-azidoethyl)cyclohex-1-ene (16) in benzene at 140-degrees-C caused the following sequence of events: (1) intramolecular 1,3-dipolar cycloaddition of the azide onto the alkene: (2) formation of an imine by loss of nitrogen from the triazoline intermediate with concomitant hydrogen migration:and (3) intramolecular N-alkylation of the imine nitrogen with the benzylic chloride. Without isolation, the resultant iminium ion was reduced with sodium borohydride to give (+/-)-gamma-lycorane (3). The cyclization precursor 16 was prepared a novel allylic substitution reaction, where the allylic alcohol 10 or the allylic acetate 11 was treated with 1-ethoxy-1-[(tert-butyldimethylsilyl)oxy]ethene and lithium perchlorate in ether to produce the gamma,delta-unsaturated ester 12. An alternative synthesis of (+/-)-gamma-lycorane (3) was accomplished using a similar 1,3-dipolar cycloaddition approach, except that the benzylic chloride functionality was absent (i.e., 26 --> 27). Reduction of the resultant imine followed by a Bischler-Napieralski cyclization gave the known lactam 31, which had previously been converted to (+/-)-gamma-lycorane.