(5R,7R)-7-(Benzoyloxy)-8,8-dimethoxy-2,2-dimethyl-1,3-dioxaspiro<4.5>decan-9-one | 164029-91-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (5R,7R)-7-(Benzoyloxy)-8,8-dimethoxy-2,2-dimethyl-1,3-dioxaspiro<4.5>decan-9-one
• 英文别名: [(5R,9R)-8,8-dimethoxy-2,2-dimethyl-7-oxo-1,3-dioxaspiro[4.5]decan-9-yl] benzoate
• CAS: 164029-91-8
• 化学式: C₁₉H₂₄O₇
• 分子量: 364.395
• InChiKey: PGXATOYVUPSUCN-QAPCUYQASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (5R,7R)-7-(Benzoyloxy)-8,8-dimethoxy-2,2-dimethyl-1,3-dioxaspiro<4.5>decan-9-one 在 氯化铵 作用下， 以 甲醇 为溶剂， 反应 84.0h， 以70%的产率得到(5R)-5-(Benzoyloxy)-3-(hydroxymethyl)-6,6-dimethoxy-2-cyclohexenone
  参考文献：
  名称：

  Transformations of Quinic Acid. Asymmetric Synthesis and Absolute Configuration of Mycosporin I and Mycosporin-gly

  摘要：

  D-(-)-Quinic acid (1) was converted to the fungal metabolites mycosporin I (2) and mycosporin-gly (13) via the iminophosphorane 64. The latter was prepared in 10 steps from 1 using oxidative bromination of quinide 33 to furnish 41. Reduction of the gamma-lactone, followed by protection of the 1,2-diol, was accompanied by migration of the benzoyl group to yield 43. The latter was oxidized to 47 which underwent displacement by sulfinate to give 59. O-Methylation, followed by reduction of the benzoate, afforded 61. Oxidation of 61 produced 62 which was converted to beta-azido enone 63. Treatment of 63 with triphenylphosphine gave crystalline 64. An aza-Wittig reaction of 64 with glyoxylate and reduction of the resultant imine yielded 68 which, after deprotection, afforded 13. Analogous coupling of 64 with diethyl ketomalonate and subsequent reduction of the ester groups led to 2. Mycosporin I and mycosporin-gly are shown by this sequence to possess S absolute configuration.

  DOI：

  10.1021/jo00117a008
• 作为产物：
  描述：

  (5S,7R,9R)-7-(Benzoyloxy)-9-hydroxy-8,8-dimethoxy-2,2-dimethyl-1,3-dioxaspiro<4.5>decane 在 sodium acetate 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以90%的产率得到(5R,7R)-7-(Benzoyloxy)-8,8-dimethoxy-2,2-dimethyl-1,3-dioxaspiro<4.5>decan-9-one
  参考文献：
  名称：

  Transformations of Quinic Acid. Asymmetric Synthesis and Absolute Configuration of Mycosporin I and Mycosporin-gly

  摘要：

  D-(-)-Quinic acid (1) was converted to the fungal metabolites mycosporin I (2) and mycosporin-gly (13) via the iminophosphorane 64. The latter was prepared in 10 steps from 1 using oxidative bromination of quinide 33 to furnish 41. Reduction of the gamma-lactone, followed by protection of the 1,2-diol, was accompanied by migration of the benzoyl group to yield 43. The latter was oxidized to 47 which underwent displacement by sulfinate to give 59. O-Methylation, followed by reduction of the benzoate, afforded 61. Oxidation of 61 produced 62 which was converted to beta-azido enone 63. Treatment of 63 with triphenylphosphine gave crystalline 64. An aza-Wittig reaction of 64 with glyoxylate and reduction of the resultant imine yielded 68 which, after deprotection, afforded 13. Analogous coupling of 64 with diethyl ketomalonate and subsequent reduction of the ester groups led to 2. Mycosporin I and mycosporin-gly are shown by this sequence to possess S absolute configuration.

  DOI：

  10.1021/jo00117a008

文献信息

• Transformations of Quinic Acid. Asymmetric Synthesis and Absolute Configuration of Mycosporin I and Mycosporin-gly
  作者：James D. White、Janice H. Cammack、Kazuhiko Sakuma、Gordon W. Rewcastle、Rexford K. Widener

  DOI：10.1021/jo00117a008

  日期：1995.6

  D-(-)-Quinic acid (1) was converted to the fungal metabolites mycosporin I (2) and mycosporin-gly (13) via the iminophosphorane 64. The latter was prepared in 10 steps from 1 using oxidative bromination of quinide 33 to furnish 41. Reduction of the gamma-lactone, followed by protection of the 1,2-diol, was accompanied by migration of the benzoyl group to yield 43. The latter was oxidized to 47 which underwent displacement by sulfinate to give 59. O-Methylation, followed by reduction of the benzoate, afforded 61. Oxidation of 61 produced 62 which was converted to beta-azido enone 63. Treatment of 63 with triphenylphosphine gave crystalline 64. An aza-Wittig reaction of 64 with glyoxylate and reduction of the resultant imine yielded 68 which, after deprotection, afforded 13. Analogous coupling of 64 with diethyl ketomalonate and subsequent reduction of the ester groups led to 2. Mycosporin I and mycosporin-gly are shown by this sequence to possess S absolute configuration.