3-[(1R,3aS,4S,5S,7aR)-1-((R)-1,5-Dimethyl-hexyl)-7a-methyl-5-((S)-3-methyl-5-oxo-[1,2]dioxolan-3-yl)-octahydro-inden-4-yl]-propionic acid methyl ester | 129270-24-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 3-[(1R,3aS,4S,5S,7aR)-1-((R)-1,5-Dimethyl-hexyl)-7a-methyl-5-((S)-3-methyl-5-oxo-[1,2]dioxolan-3-yl)-octahydro-inden-4-yl]-propionic acid methyl ester
• 英文别名: methyl 3-[(1R,3aS,4S,5S,7aR)-7a-methyl-1-[(2R)-6-methylheptan-2-yl]-5-[(3S)-3-methyl-5-oxodioxolan-3-yl]-1,2,3,3a,4,5,6,7-octahydroinden-4-yl]propanoate
• CAS: 129270-24-2
• 化学式: C₂₆H₄₄O₅
• 分子量: 436.632
• InChiKey: PDWMXZWWDYJWKU-ASRVECIMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  31
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-[(1R,3aS,4S,5S,7aR)-1-((R)-1,5-Dimethyl-hexyl)-7a-methyl-5-((S)-3-methyl-5-oxo-[1,2]dioxolan-3-yl)-octahydro-inden-4-yl]-propionic acid methyl ester 在 重氮甲烷 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 生成 3-[(1R,3aS,4S,7aR)-1-((R)-1,5-Dimethyl-hexyl)-7a-methyl-octahydro-inden-4-yl]-propionic acid methyl ester 、 (S)-3-[(1R,3aS,4S,5S,7aR)-1-((R)-1,5-Dimethyl-hexyl)-4-(2-methoxycarbonyl-ethyl)-7a-methyl-octahydro-inden-5-yl]-3-hydroxy-butyric acid methyl ester
  参考文献：
  名称：

  Tandem Carbon-Radical Peroxidation-Addition to Carbonyl Groups Reaction. A New Synthesis of Steroidal .beta.-Peroxy Lactones

  摘要：

  A mild and efficient synthesis of beta-peroxy lactones by alkoxy radical beta-fragmentation reaction of gamma-hydroxy carbonyl compounds is described. Steroidal models 5-hydroxy-4-nor-3-oxa-5 alpha-cholestan-2-one (1), 5-hydroxy-5 alpha-cholestan-2-one (2), and 5,17 beta-dihydroxy-4-nor-5 alpha-androstan-2-one 17-acetate (3) were synthesized to test the present methodology. These substrates are subjected to photolysis with visible light in the presence of (diacetoxyiodo)benzene, lead tetraacetate, or HgO, I-2, and molecular oxygen to generate the corresponding alkoxy radical. The fragmentation of this radical results in the carbon radical which is trapped by molecular oxygen in the key step to generate a peroxy radical. Intramolecular addition of this peroxy radical to the carbonyl group present in the molecule is followed by beta-fragmentation to yield the peroxy lactone radical. Subsequent trapping of this radical results in stable peroxy lactone. In all cases, regiospecific beta-fragmentations and stereoselective peroxidation at C-10 radical were observed. This operationally simple multistep radical procedure permitted us to synthesize steroidal beta-peroxy lactones 8, 12, and 15 in moderate to good yields.

  DOI：

  10.1021/jo00130a020
• 作为产物：
  描述：

  5-hydroxy-4-nor-3-oxa-5α-cholestan-2-one 在 lead(IV) acetate 、 air 、 碘 作用下， 以 乙醚 、 环己烷 为溶剂， 40.0 ℃ 、101.33 kPa 条件下， 反应 3.0h， 生成 3-[(1R,3aS,4S,5S,7aR)-1-((R)-1,5-Dimethyl-hexyl)-7a-methyl-5-((S)-3-methyl-5-oxo-[1,2]dioxolan-3-yl)-octahydro-inden-4-yl]-propionic acid methyl ester
  参考文献：
  名称：

  Tandem Carbon-Radical Peroxidation-Addition to Carbonyl Groups Reaction. A New Synthesis of Steroidal .beta.-Peroxy Lactones

  摘要：

  A mild and efficient synthesis of beta-peroxy lactones by alkoxy radical beta-fragmentation reaction of gamma-hydroxy carbonyl compounds is described. Steroidal models 5-hydroxy-4-nor-3-oxa-5 alpha-cholestan-2-one (1), 5-hydroxy-5 alpha-cholestan-2-one (2), and 5,17 beta-dihydroxy-4-nor-5 alpha-androstan-2-one 17-acetate (3) were synthesized to test the present methodology. These substrates are subjected to photolysis with visible light in the presence of (diacetoxyiodo)benzene, lead tetraacetate, or HgO, I-2, and molecular oxygen to generate the corresponding alkoxy radical. The fragmentation of this radical results in the carbon radical which is trapped by molecular oxygen in the key step to generate a peroxy radical. Intramolecular addition of this peroxy radical to the carbonyl group present in the molecule is followed by beta-fragmentation to yield the peroxy lactone radical. Subsequent trapping of this radical results in stable peroxy lactone. In all cases, regiospecific beta-fragmentations and stereoselective peroxidation at C-10 radical were observed. This operationally simple multistep radical procedure permitted us to synthesize steroidal beta-peroxy lactones 8, 12, and 15 in moderate to good yields.

  DOI：

  10.1021/jo00130a020

文献信息

• Tandem Carbon-Radical Peroxidation-Addition to Carbonyl Groups Reaction. A New Synthesis of Steroidal .beta.-Peroxy Lactones
  作者：Alicia Boto、Rosendo Hernandez、Ernesto Suarez、Carmen Betancor、Maria S. Rodriguez

  DOI：10.1021/jo00130a020

  日期：1995.12

  A mild and efficient synthesis of beta-peroxy lactones by alkoxy radical beta-fragmentation reaction of gamma-hydroxy carbonyl compounds is described. Steroidal models 5-hydroxy-4-nor-3-oxa-5 alpha-cholestan-2-one (1), 5-hydroxy-5 alpha-cholestan-2-one (2), and 5,17 beta-dihydroxy-4-nor-5 alpha-androstan-2-one 17-acetate (3) were synthesized to test the present methodology. These substrates are subjected to photolysis with visible light in the presence of (diacetoxyiodo)benzene, lead tetraacetate, or HgO, I-2, and molecular oxygen to generate the corresponding alkoxy radical. The fragmentation of this radical results in the carbon radical which is trapped by molecular oxygen in the key step to generate a peroxy radical. Intramolecular addition of this peroxy radical to the carbonyl group present in the molecule is followed by beta-fragmentation to yield the peroxy lactone radical. Subsequent trapping of this radical results in stable peroxy lactone. In all cases, regiospecific beta-fragmentations and stereoselective peroxidation at C-10 radical were observed. This operationally simple multistep radical procedure permitted us to synthesize steroidal beta-peroxy lactones 8, 12, and 15 in moderate to good yields.