(4S)-4-Carbomethoxy-2,2-dimethyl-4-<(1R)-1,5-dimethyl-4-hexenyl>-1,3-dioxolane | 122445-39-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4S)-4-Carbomethoxy-2,2-dimethyl-4-<(1R)-1,5-dimethyl-4-hexenyl>-1,3-dioxolane
• 英文别名: (4S)-4-Carbomethoxy-2,2-dimethyl-4-((1R)-1,5-dimethyl-4-hexenyl)-1,3-dioxolane；methyl (4S)-2,2-dimethyl-4-[(2R)-6-methylhept-5-en-2-yl]-1,3-dioxolane-4-carboxylate
• CAS: 122445-39-0
• 化学式: C₁₅H₂₆O₄
• 分子量: 270.369
• InChiKey: GPFCXXCLVLEVRK-IUODEOHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.06
• 重原子数：
  19.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  44.76
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (4S)-4-Carbomethoxy-2,2-dimethyl-4-<(1R)-1,5-dimethyl-4-hexenyl>-1,3-dioxolane 在 4-二甲氨基吡啶 、 ruthenium trichloride 、 titanium(IV) tetraethanolate 、 sodium periodate 、 正丁基锂 、 二甲基硫 、 氢氟酸 、 四丁基氟化铵 、 臭氧 、 甲基磺酰氯 、 三乙胺 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 四氯化碳 、 二氯甲烷 、 乙腈 为溶剂， 反应 86.25h， 生成 (1'R,4S,6'R,17'R)-2,2,6'-trimethylspiro[1,3-dioxolane-4,7'-2,9-dioxa-14-azatricyclo[9.5.1.014,17]heptadec-11-ene]-3',8'-dione
  参考文献：
  名称：

  Stereoselective synthesis of the pyrrolizidine alkaloids (-)-integerrimine and (+)-usaramine

  摘要：

  Two routes to the pyrrolizidine alkaloid (-)-integerrimine (1) are described. The first, starting from methyl (R)-(-)-3-hydroxy-2-methylpropionate, proceeded in 19 steps to integerrinecic acid lactone (5) which was transformed to the necic acid derivative 30. The latter was coupled to protected retronecine 31, and the synthesis of 1 was completed by lactonization employing Vedejs' protocol. A second, shorter synthesis of (-)-1 was accomplished via 5, starting from (R)-(+)-beta-citronellol (36). This pathway invoked Katsuki-Sharpless epoxidation of 42 for stereoselective construction of the tertiary alcohol of integerrinecic acid. A parallel sequence proceeding via the stereoisomeric epoxide 44 led to the necic acid segment 75 of the alkaloid (+)-usaramine (2). This acid was coupled to the retronecine borane 82 and then lactonized to 2.

  DOI：

  10.1021/jo00034a017
• 作为产物：
  描述：

  (2S,3R)-3,7-Dimethyl-2-hydroxy-2-(hydroxymethyl)-6-octenyl Pivalate 在 lithium aluminium tetrahydride 、 重铬酸吡啶 、 camphor-10-sulfonic acid 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 36.0h， 生成 (4S)-4-Carbomethoxy-2,2-dimethyl-4-<(1R)-1,5-dimethyl-4-hexenyl>-1,3-dioxolane
  参考文献：
  名称：

  Stereoselective synthesis of the pyrrolizidine alkaloids (-)-integerrimine and (+)-usaramine

  摘要：

  Two routes to the pyrrolizidine alkaloid (-)-integerrimine (1) are described. The first, starting from methyl (R)-(-)-3-hydroxy-2-methylpropionate, proceeded in 19 steps to integerrinecic acid lactone (5) which was transformed to the necic acid derivative 30. The latter was coupled to protected retronecine 31, and the synthesis of 1 was completed by lactonization employing Vedejs' protocol. A second, shorter synthesis of (-)-1 was accomplished via 5, starting from (R)-(+)-beta-citronellol (36). This pathway invoked Katsuki-Sharpless epoxidation of 42 for stereoselective construction of the tertiary alcohol of integerrinecic acid. A parallel sequence proceeding via the stereoisomeric epoxide 44 led to the necic acid segment 75 of the alkaloid (+)-usaramine (2). This acid was coupled to the retronecine borane 82 and then lactonized to 2.

  DOI：

  10.1021/jo00034a017

文献信息

• Synthesis of the macrolactone alkaloid (+)-usaramine via necic acid coupling to a pyrrolizidine borane
  作者：James D. White、John C. Amedio、Samuel Gut、Lalith Jayasinghe

  DOI：10.1021/jo00279a005

  日期：1989.9
• WHITE, JAMES D.;AMEDIO, JOHN C. (JR);GUT, SAMUEL;JAYASINGHE, LALITH, J. ORG. CHEM., 54,(1989) N8, C. 4268-4270
  作者：WHITE, JAMES D.、AMEDIO, JOHN C. (JR)、GUT, SAMUEL、JAYASINGHE, LALITH

  DOI：——

  日期：——