(4aR,6R,6aS,7aR,10aR,10bR,10cS)-6-Benzyloxy-9,9-dimethyl-decahydro-7,8,10-trioxa-pentaleno[1,2-a]naphthalen-1-one | 142186-75-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并呋喃类
• 英文名称: (4aR,6R,6aS,7aR,10aR,10bR,10cS)-6-Benzyloxy-9,9-dimethyl-decahydro-7,8,10-trioxa-pentaleno[1,2-a]naphthalen-1-one
• 英文别名: (1R,2S,7R,9R,10S,12R,16R)-14,14-dimethyl-9-phenylmethoxy-11,13,15-trioxatetracyclo[8.6.0.02,7.012,16]hexadecan-3-one
• CAS: 142186-75-2
• 化学式: C₂₂H₂₈O₅
• 分子量: 372.461
• InChiKey: HRPQUBLWPAQSOY-CBSPIHFOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.68
• 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：

  (4aR,6R,6aS,7aR,10aR,10bR,10cS)-6-Benzyloxy-9,9-dimethyl-decahydro-7,8,10-trioxa-pentaleno[1,2-a]naphthalen-1-one 在 间氯过氧苯甲酸 作用下， 以41%的产率得到(1R,2S,8R,10R,11S,13R,17R)-15,15-dimethyl-10-phenylmethoxy-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
• 作为产物：
  描述：

  (4aS,6R,6aS,7aR,10aR,10bR,10cS)-6-Benzyloxy-1-methoxy-9,9-dimethyl-4a,5,6,6a,7a,10a,10b,10c-octahydro-4H-7,8,10-trioxa-pentaleno[1,2-a]naphthalen-3-one 在 镍 氢气 、 二异丁基氢化铝 作用下， 生成 (4aR,6R,6aS,7aR,10aR,10bR,10cS)-6-Benzyloxy-9,9-dimethyl-decahydro-7,8,10-trioxa-pentaleno[1,2-a]naphthalen-1-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.