(1S,2S,6S,8S,11R,13R,17R)-6,15,15-trimethyl-3,12,14,16-tetraoxatetracyclo[9.6.0.02,8.013,17]heptadecan-4-one | 142186-71-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (1S,2S,6S,8S,11R,13R,17R)-6,15,15-trimethyl-3,12,14,16-tetraoxatetracyclo[9.6.0.02,8.013,17]heptadecan-4-one
• CAS: 142186-71-8
• 化学式: C₁₆H₂₄O₅
• 分子量: 296.364
• InChiKey: QAROVYFLYHCFLJ-GMGUOPGQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 (1S,2S,6S,8S,11R,13R,17R)-6,15,15-trimethyl-3,12,14,16-tetraoxatetracyclo[9.6.0.02,8.013,17]heptadecan-4-one 在 lithium aluminium tetrahydride 作用下， 生成 Acetic acid (3aR,4aR,7S,8S,8aS,8bR)-7-((S)-4-acetoxy-2-methyl-butyl)-2,2-dimethyl-octahydro-benzo[4,5]furo[2,3-d][1,3]dioxol-8-yl ester
  参考文献：
  名称：

  Tandem intramolecular Michael addition/aldol condensation or acylation applied to D-glucose-derived substrates: preparation of enantiomeric octahydronaphthalenone derivatives equipped with C- and O-functionalities

  摘要：

  An enantiomerically pure (1,2-isopropylidenedioxy)tetrahydrofuran derivative, 9, bearing acetonyl and propionaldehyde side chains smoothly underwent aldol cyclization under basic conditions. The major product was the cis-aldol 21S, accompanied by the trans-diastereomer 21R in a ratio of 4 to 1. Further functionalized substrates 10 and 11, with either a (4-acetyl)- or a (4-ethoxycarbonyl)-3(E)-butenyl group, smoothly underwent a tandem Michael addition/aldol condensation or acylation by treatment with sodium hydride (NaH). In the case of 10, two cis-fused octahydronaphthalenones, 23 and 25, and a trans-fused diasteromer, 24, were isolated in 20%, 33%, and 11% yields, respectively. The substrate 11 provided a cis-substituted perhydrobenzofuran derivative, 26, and cis- and trans-fused octahydronaphthalenediones, 27 and 28, in 52%, 17%, and 9% yields, respectively. An intramolecular S(N)2' type cyclization of the corresponding 5-chloro-3(E)-pentenyl derivative, 14, provided exclusively (96%) the perhydrobenzofuran derivative, 29, in which the two newly introduced substituents are disposed in a cis relationship. The stereochemical assignments for each cyclization product were achieved by H-1 NMR analysis of the cyclization products or their chemically modified compounds. Preferential formation of the cis-fused carbocycles in the present studies is rationalized from a stereoelectronic viewpoint. Furthermore, the effect of substituents on the cyclization was investigated using two tetrahydrofuran derivatives, 20S and 20R. Base treatment of 20S gave the cis-fused tandem cyclization product 30 and the trans diastereomer 31 in a ratio of 3.8 to 1. In contrast, 20R gave two cyclization products, 32 and 33, in a ratio of 5 to 1, as a result of a preferential trans cyclization mode.

  DOI：

  10.1021/jo00042a034
• 作为产物：
  描述：

  (3S,4aS,6aR,7aR,10aR,10bR,10cS)-3,9,9-Trimethyl-decahydro-7,8,10-trioxa-pentaleno[1,2-a]naphthalen-1-one 在 间氯过氧苯甲酸 作用下， 以87%的产率得到(1S,2S,6S,8S,11R,13R,17R)-6,15,15-trimethyl-3,12,14,16-tetraoxatetracyclo[9.6.0.02,8.013,17]heptadecan-4-one
  参考文献：
  名称：

  Tandem intramolecular Michael addition/aldol condensation or acylation applied to D-glucose-derived substrates: preparation of enantiomeric octahydronaphthalenone derivatives equipped with C- and O-functionalities

  摘要：

  An enantiomerically pure (1,2-isopropylidenedioxy)tetrahydrofuran derivative, 9, bearing acetonyl and propionaldehyde side chains smoothly underwent aldol cyclization under basic conditions. The major product was the cis-aldol 21S, accompanied by the trans-diastereomer 21R in a ratio of 4 to 1. Further functionalized substrates 10 and 11, with either a (4-acetyl)- or a (4-ethoxycarbonyl)-3(E)-butenyl group, smoothly underwent a tandem Michael addition/aldol condensation or acylation by treatment with sodium hydride (NaH). In the case of 10, two cis-fused octahydronaphthalenones, 23 and 25, and a trans-fused diasteromer, 24, were isolated in 20%, 33%, and 11% yields, respectively. The substrate 11 provided a cis-substituted perhydrobenzofuran derivative, 26, and cis- and trans-fused octahydronaphthalenediones, 27 and 28, in 52%, 17%, and 9% yields, respectively. An intramolecular S(N)2' type cyclization of the corresponding 5-chloro-3(E)-pentenyl derivative, 14, provided exclusively (96%) the perhydrobenzofuran derivative, 29, in which the two newly introduced substituents are disposed in a cis relationship. The stereochemical assignments for each cyclization product were achieved by H-1 NMR analysis of the cyclization products or their chemically modified compounds. Preferential formation of the cis-fused carbocycles in the present studies is rationalized from a stereoelectronic viewpoint. Furthermore, the effect of substituents on the cyclization was investigated using two tetrahydrofuran derivatives, 20S and 20R. Base treatment of 20S gave the cis-fused tandem cyclization product 30 and the trans diastereomer 31 in a ratio of 3.8 to 1. In contrast, 20R gave two cyclization products, 32 and 33, in a ratio of 5 to 1, as a result of a preferential trans cyclization mode.

  DOI：

  10.1021/jo00042a034

文献信息

• Tandem intramolecular Michael addition/aldol condensation or acylation applied to D-glucose-derived substrates: preparation of enantiomeric octahydronaphthalenone derivatives equipped with C- and O-functionalities
  作者：Kinichi Tadano、Kensuke Nagashima、Yoshihide Ueno、Seiichiro Ogawa

  DOI：10.1021/jo00042a034

  日期：1992.7

  An enantiomerically pure (1,2-isopropylidenedioxy)tetrahydrofuran derivative, 9, bearing acetonyl and propionaldehyde side chains smoothly underwent aldol cyclization under basic conditions. The major product was the cis-aldol 21S, accompanied by the trans-diastereomer 21R in a ratio of 4 to 1. Further functionalized substrates 10 and 11, with either a (4-acetyl)- or a (4-ethoxycarbonyl)-3(E)-butenyl group, smoothly underwent a tandem Michael addition/aldol condensation or acylation by treatment with sodium hydride (NaH). In the case of 10, two cis-fused octahydronaphthalenones, 23 and 25, and a trans-fused diasteromer, 24, were isolated in 20%, 33%, and 11% yields, respectively. The substrate 11 provided a cis-substituted perhydrobenzofuran derivative, 26, and cis- and trans-fused octahydronaphthalenediones, 27 and 28, in 52%, 17%, and 9% yields, respectively. An intramolecular S(N)2' type cyclization of the corresponding 5-chloro-3(E)-pentenyl derivative, 14, provided exclusively (96%) the perhydrobenzofuran derivative, 29, in which the two newly introduced substituents are disposed in a cis relationship. The stereochemical assignments for each cyclization product were achieved by H-1 NMR analysis of the cyclization products or their chemically modified compounds. Preferential formation of the cis-fused carbocycles in the present studies is rationalized from a stereoelectronic viewpoint. Furthermore, the effect of substituents on the cyclization was investigated using two tetrahydrofuran derivatives, 20S and 20R. Base treatment of 20S gave the cis-fused tandem cyclization product 30 and the trans diastereomer 31 in a ratio of 3.8 to 1. In contrast, 20R gave two cyclization products, 32 and 33, in a ratio of 5 to 1, as a result of a preferential trans cyclization mode.